Computational Studies on the Molecule 1-(2-Hydroxyethyl)-5 ...downloads.hindawi.com/journals/acmp/2019/1706926.pdfAdvancesinCondensedMatterPhysics thuso eringthepossibilityofusingthemingenetherapy

Research ArticleComputational Studies on the Molecule1-(2-Hydroxyethyl)-5-Fluorouracil in Gas Phaseand Aqueous Solution and Prediction of ItsConfinement inside Capped Nanotubes

Y Tadjouteu Assatse 1 G W Ejuh 23 F Tchoffo1 and J M B Ndjaka 1

1University of Yaounde I Faculty of Science Department of Physics Materials Science Laboratory PO Box 812 Yaounde Cameroon2University of Dschang IUT Bandjoun Department of General and Scientific Studies PO Box 134 Bandjoun Cameroon3University of Bamenda National Higher Polytechnic Institute Department of Electrical and Electronic EngineeringPO Box 39 Bambili Cameroon

Correspondence should be addressed to Y Tadjouteu Assatse yannicktadjouteyahoofr

Received 12 March 2019 Revised 31 May 2019 Accepted 11 June 2019 Published 4 August 2019

Academic Editor Charles Rosenblatt

Copyright copy 2019 Y Tadjouteu Assatse et al This is an open access article distributed under the Creative Commons AttributionLicense which permits unrestricted use distribution and reproduction in any medium provided the original work is properlycited

Density functional theory (DFT) calculations were performed on a fluorouracil derivative at the B3LYP6minus31+G(d) levelFurthermore the ONIOM method was performed to investigate the possibility of its confinement inside capped nanotubes Theresults found of the structural parameters of the optimized molecule are in good agreement with experimental dataThe analysis ofthermodynamic properties leads us to predict that the confinement of the studiedmolecule inside capped nanotubes SWCNT(120)SWCNT(140) and SWCNT(160) is possible The large 119864119892 values found suggest a good stability for the studied molecule Thepredicted nonlinear optical (NLO) properties of the studied molecule are much greater than those of urea Thereby it is a goodcandidate as second-order NLO material The calculated 119866119904119900119897 values suggest that the studied molecule is more soluble than the5-FU molecule The results of quantum molecular descriptors show that the studied molecule is hard electrophile and stronglyreactive

1 Introduction

Experimental and theoretical studies have been previouslydone on the molecule uracil and its derivatives [1] espe-cially the anticarcinogenic drug 5-fluorouracil (5-FU) [2]employed for treating solids tumors especially those ofgastrointestinal tract brain breast pancreas and liver [3]One of the 5-FU derivatives recently characterized by X-raydiffraction is the molecule 1-(2-hydroxyethyl)-5-fluorouracil[4] A good understanding of properties of molecules withtherapeutic effects is very crucial as well as their directdelivery to the right target The study of interactions betweennanostructures and therapeutic molecules is very importantfor the carrying and targeted delivery of drugs and otherbiomolecules Various types of hybrid nanostructures mod-eled by the interaction of therapeutic molecules or chemical

substances with nanometric structures such as phagraphene[5] fullerenes [6] and boron nitride nanoparticles [7] havebeen reported in the literature These nanostructures canalso be very important for applications such as the designof sensor systems [8] and energy storage devices [9] Thecarbon nanotube is one of the most popular nanostructuresused as nanocarrier on the basis of interactions with chemicalcompounds

The confinement of molecules inside carbon nanotubesremains a big challenge The confinement of therapeuticmolecules inside nanotubes is very interesting due to the factthat the nanotube protects the biologically active moleculefrom degradation and the hybrid nanostructure formed bythe nanotube and the confined molecule can overcome theresistance of mechanical physicochemical and enzymaticbarriers Nanotubes can even cross biological barriers [10]

HindawiAdvances in Condensed Matter PhysicsVolume 2019 Article ID 1706926 14 pageshttpsdoiorg10115520191706926

2 Advances in Condensed Matter Physics

thus offering the possibility of using them in gene therapyZare et al [11] have reported a research work on thecomparison of drug delivery systems They have shown thatcarbon nanotubes deliver the 5-FU molecule better than thep-sulfonatocalix-[4]-arene Carbon nanotubes have a greatpotential to carry molecules Many studies on medical andbiomedical applications [12 13] of carbon nanotubes havebeen reported in the literature Robinson et al [14] havedeveloped a generalized numerical method for generating theatomic coordinates of nanotube caps

Many computational methods [15] have been developedto investigate the properties of molecules Density functionaltheory (DFT) is greatly used in molecular computationalstudy This computational method reproduces very well theexperimental properties of molecules such as geometricalstructures vibrational properties and nonlinear and elec-tronic properties [16 17] Recently it has been reported thatthe van der Waals interactions play a major role in theencapsulation of molecules inside carbon nanotubes [18]Thevan der Waals interactions can be taken into considerationin the modeling of hybrid nanostructures using the quantummechanics (QM)molecular mechanics (MM) calculationsespecially the ONIOM method The ONIOM method [19]has proved to be a powerful tool in combining quantummechanics and molecular mechanics calculations Chung etal [20] have reported a review on theONIOMmethod and itsapplications In their review many theoretical investigationsusing ONIOM methods on the encapsulation of moleculesinside carbon nanotubes and other nanostructures have beenreported In particular Garcia et al [21] have studied theconfinement of 120573-carotene inside carbon nanotubes usingan ONIOM method Ahmadi et al [22] have studied theadsorption of ammonia molecules inside aluminum nitridenanotubes using an ONIOM method To experimentallyencapsulate a drug into a capped carbon nanotube thefirst step is to synthesize the carbon nanotube [23] As thesynthesized nanotubes are usually closed by domes at leastone end must be opened before incorporation of the drugThe opening of the nanotube can be done by chemicaloxidation [24] or thermal oxidation [25] Yudasaka et al [26]have developed two different methods called nanoextractionand nanocondensation to incorporate guest molecules intosingle-walled carbon nanotubes in liquid phases Ren et al[27] have applied the nanoextraction method to incorpo-rate the antitumor agent hexamethylmelamine into carbonnanotubes Recently Wu et al [28] have also used thenanoextraction method to incorporate the antitumor agentoxaliplatin into multiwalled carbon nanotubes Satishkumaret al [24] have reported experimental methods for closingcarbon nanotubes They have experimentally shown thatuncapped nanotubes can be closed by the reaction at hightemperature with benzene vapour in a reducing atmosphereof hydrogen and argon

To the best of our knowledge this is the first theoreticalstudy on themolecule 1-(2-hydroxyethyl)-5-fluorouracil pub-lished The aim of this work is to investigate the properties ofthe molecule 1-(2-hydroxyethyl)-5-fluorouracil in gas phaseand aqueous solution Furthermore the changes occurring inthe molecular geometrical structure and the thermodynamic

stability when it is confined inside the hollow space of cappednanotubes SWCNT(120) SWCNT(140) and SWCNT(160)by considering mainly the van der Waals interaction havebeen investigated This study is performed to predict theencapsulation of this molecule into carbon nanotubes thelong-term objective is to perform a targeted delivery of thismolecule in cancer cells following the model proposed byHilder et al [29] In this study the molecular structureanalysis of the studied molecule has been performed ingas phase and aqueous solution by a DFT method andinside the nanotube cavity by anONIOM(DFTMM)methodThe thermodynamic properties of the studied moleculeand the thermodynamic stability study of the optimizedhybrid nanostructures have been investigated at differenttemperatures The vibrational analysis the nonlinear andelectronic properties the Gibbs free energy of solvation andthe quantum molecular descriptors of the studied moleculehave been investigated in gas phase and aqueous solution

2 Computational Methodology

Density functional theory (DFT) was performed for thecalculations of properties of the studied molecule in gasphase and aqueous solution while the ONIOM(DFTMM)method was performed to study the hybrid nanostructuresThe hybrid nanostructures were obtained by the confinementof the studied molecule inside the nanotube cavities Weused capped nanotubes SWCNT(120) SWCNT(140) andSWCNT(160) of 336 428 and 488 carbon atoms respec-tively The diameters of these nanotubes are 9402 A 10968A and 12536 AThese nanotubes were chosen to point up thediameter range of carbon nanotubes that allow the studiedmolecule to be confined without any significant moleculargeometry alterationThe uncapped nanotubes SWCNT(120)SWCNT(140) and SWCNT(160) have a finite length of 1739A and they have 204 238 and 272 carbon atoms respectivelyEach cap of these nanotubes was formed with pentagonaldefects The 2D projections of the capped nanotubes areshown in Figure 1(a) The full geometry optimizations wereperformed on the studied molecule and the hybrid nanos-tructures using Gaussian 09 W program [30] The results ofsimulations were visualized by GaussView 5 program [31]We used the functional B3LYP with the 6minus31+G(d) basis setto implement DFT calculations The polarizable continuummodel with a conductor solvent model (CPCM) was appliedto account for solvation effects In our calculations water(dielectric constant (120576) of 784)was used as solvatingmediumThe Gibbs free energy of solvation was calculated by takingthe difference between the total electronic energy in waterafter polarized continuum model (PCM) corrections usingthe SMD continuum model [32] and the total electronicenergy in gas phase

The inclusion of vanderWaals (vdW) interactions [18] foran accurate description of the molecular structure of nanos-tructures designed by encapsulation of molecule inside thehollow space of nanotube is indispensable The combinationof DFT with the united force field (UFF) has been widelyused [33 34] The noncovalent interactions were applied

Advances in Condensed Matter Physics 3

capped-SWCNT(120) capped-SWCNT(140) capped-SWCNT(160)

(a) (b)

encapsulated capped-SWCNT(120) encapsulated capped-SWCNT(140) encapsulated capped-SWCNT(160)

(c)

Figure 1 (a) 2D projection of capped nanotubes SWCNT(120) SWCNT(140) and SWCNT(160) (b)The molecular geometrical structureof the studied molecule in gas phase (c) The optimized hybrid nanostructures by the confinement of the studied molecule inside nanotubecavities of capped SWCNT(120) SWCNT(140) and SWCNT(160)

during the optimization of the hybrid nanostructures withthe ONIOM method by combining the B3LYP6minus31+G(d)level with the united force field (UFF) The stability constantand thermodynamic quantities such as enthalpy Gibbs freeenergy and entropy were computed to analyze the stabilityof the optimized hybrid nanostructures The use of local-ized basis sets reduces the amount of computational workrequired However calculations using finite basis sets aresusceptible to basis set superposition errors (BSSEs) Thechanges of energies in all complexes nanostructures werecorrected by calculating the basis set superposition errorusing the counterpoisemethod [35] In thismethod the BSSEis calculated using the mixed basis sets and the error isthen subtracted a posteriori from the uncorrected energyThemixed basis sets are realized by introducing ldquoghost orbitalsrdquo(basis set functions which have no electrons or protons)

Unscaled vibrational properties of the studied moleculewere computed in gas phase and aqueous solution Thenonlinear and electronic properties were calculated usingthe optimized molecular structure A dipole moment canbe induced through the electric polarizability 120572 under theinfluence of an external electric field E For an intense electricfield Ei(120596) the total dipole moment can be written as a Taylorseries expansion induced by the field

120583tot = 1205830 + 120572ijEj + 120573ijkEjEk + sdot sdot sdot (1)

where 1205830 is the permanent dipole moment and 120572ij and120573ijk are the components of the polarizability and first-orderhyperpolarizability respectively The total dipole moment(120583tot) the mean polarizability (120572m) and the static first-orderhyperpolarizability (120573m) are calculated from the Gaussian


output by using the equations found in the literature [36]The total density of states (DOS) of the studied moleculewas plotted with the data of molecular orbitals obtainedusing GaussSum 22 program [37] The difference betweenthe energies of the LUMO and HOMO orbitals correspondsto the energy gap Furthermore the HOMO energy (EH)and LUMO energy (EL) were used to calculate the quantummolecular descriptors The ionization potential (IP) andthe electron affinity (EA) were derived from the frontiermolecular orbital energies using the following relationsrespectively IP = minusEH and EA = minusEL The hardness (120578)softness (S) electronegativity (120594) chemical potential (120583) andelectrophilicity index (120596) were calculated using the equationsreported in the literature [38]

The molecular electrostatic potential (MEP) is related tothe electronic density It is a very useful descriptor in under-standing sites for electrophilic attack nucleophilic reactionsand intermolecular interactions with other molecular com-pounds The molecular electrostatic potential 119881(119903) created atany given point 119903(119909 119910 119911) in the vicinity of a molecule by itselectrons and nuclei is found by

V (r) = sumA

ZA(RA minus r) minus int

120588 (r1015840)1003816100381610038161003816r1015840 minus r1003816100381610038161003816

dr1015840 (2)

where ZA is the charge of nucleus A located at RA 120588(r1015840) isthe electronic density function for the molecule and r1015840 is thedummy integration variable [39]

3 Results and Discussion

31 Optimized Structure The optimized geometrical param-eters of the studied molecule in gas phase aqueous solutionand the hollow space of the capped nanotubes SWCNT(120)SWCNT(140) and SWCNT(160) are gathered in Table 1The molecular structure of the studied molecule and theoptimized hybrid nanostructures are shown in Figures 1(b)and 1(c) respectively The computed bond lengths of thestudied molecule in gas phase and aqueous solution andinside the capped nanotubes change slightly in comparison toexperimental values of the crystal structure [4] The changesof structural parameters of the studied molecule in aqueoussolution in comparison to those in gas phase are induced bythe dipolar interaction between it and the solvating mediumInside the nanotube cavity the van der Waals interactionsapplied between the confined molecule and the nanotubecontribute mainly to the changes of structural parameters ofthe studied molecule in comparison to those in gas phase

The maximum difference between the theoretical andexperimental bond lengths is found at C8minusC9 bond Thebond lengths N1minusC10 N1minusC7 N2minusC10 N2minusC9 and C8minusC9in the gas phase and aqueous solution and inside nanotubesare close to the experimental values of the studied moleculeand slightly lower than the corresponding experimentalbonds of the 5-fluorouracil (5-FU) molecule [2] The bondsO4minusC10 and O5minusC9 are very close to the experimentalvalues of the studied molecule and slightly greater than thecorresponding experimental bonds of the 5-FUmolecule [2]

As illustrated in Table 1 most computed angles areslightly different from experimental ones In comparisonto experimental bond angles the maximum shifts occur atC10minusN1minusC11 bond angle in gas phase and at N1minusC11minusC12bond angle in aqueous solution and inside nanotubes Themost discrepancy between the studied fluorouracil derivativeand the 5-FUmolecule occurs at the N2minusC9minusC8 bond angleThus the replacement of the hydrogen atom in the 5-FUmolecule at the position N1 by the 1-(2-hydroxyethyl) frag-ment induces changes of molecular geometrical parametersof the pyrimidine ring The dihedral angles N1minusC11minusC12minus06of the confined molecule are 94223∘ 52307∘ and 51057and the dihedral angles C11minusC12minus06minusH14 are minus54497∘41838∘ and 35051∘ inside SWCNT(120) SWCNT(140)and SWCNT(160) respectively Clearly the structure of thestudied molecule can be affected by the confinement intothe capped nanotube SWCNT(120) because the dihedralangles N1minusC11minusC12minus06 and C11minusC12minus06minusH14 of the isolatedmolecule are 50822∘ and 37769∘ respectivelyWhen the stud-ied molecule is confined inside the nanotube SWCNT(140)or SWCNT(160) its structural parameters are not evi-dently affected by the nanotube The geometries of theconfined molecule inside SWCNT(140) and SWCNT(160)are very similar to those of the isolated molecule Theconfined molecule approximately locates in the middle axisof SWCNT(120) and SWCNT(140) but it is in the side ofSWCNT(160) We can conclude that any nanotube whosediameter is greater than 10968 A will have no signifi-cant influence on the geometry of the studied moleculeHowever nanotubes whose diameter is less than 9402 Acan significantly change or destroy the molecular structureof the confined molecule The results found for structuralparameters of the studied molecule are in good agreementwith X-ray crystallographic data [4]

32 Thermodynamic Properties of the Studied Molecule andThermodynamic Stability Study of the Optimized HybridNanostructures The vibrational analysis and statistical ther-modynamics were applied to compute the standard thermo-dynamic properties of the studied molecule The computedthermodynamic properties namely enthalpy (H0m) Gibbsfree energy (G0m) and entropy (S0m) are gathered in Supple-mentary Material S1 Figure 2 shows the changes of H0m G

0m

and S0m with the temperature As illustrated in Figure 2 thevalues of H0m and S0m increase while the G0m values decreasewith the increasing of the temperature from 50 to 950 KThese changes occur because the intensities of the molecularvibrations increase with the increasing temperature Thequadratic correlation equations of the studied molecule aregiven below

H0m = 000017T2 + 007498T + 36419947(R2 = 099951)

(3)

G0m = minus000026T2 minus 027335T + 37509083(R2 = 099995)

(4)


Table1Molecular

geom

etric

alparameterso

fthe

studied

moleculeingasp

haseaqu

eous

solutio

nandtheh

ollowspaceo

fthe

nano

tubesS

WCN

T(120)SW

CNT(140)andSW

CNT(160)

Gas

Phase

Aqueou

ssolutio

nInsid

ecapp

ed-SWCN

T(120)

Insid

ecapp

ed-SWCN

T(140)

Insid

ecapp

ed-SWCN

T(160)

Experim

ental

[4]

B3LY

P6minus

31+G

(d)

B3LY

P6minus

31+G

(d)

ONIO

M(B3LYP

6minus31

+G(d)U

FF)

ONIO

M(B3LYP

6minus31

+G(d)U

FF)

ONIO

M(B3LYP

6minus31

+G(d)U

FF)

Bond

lengths

(A)

N1-C

1013

9213

8813

8213

9313

911373(3)

N1-C

713

8213

7713

8113

8113

821376(3)

N1-C

1114

7114

7614

8114

7014

721479(3)

N2-C1

013

8413

8513

8013

8513

841374(3)

N2-C9

1407

1397

1405

1407

1408

1385(3)

F3-C

813

4513

5213

4313

4513

441355(3)

O4-C1

012

2812

3112

2812

2712

281228(3)

O5-C9

1219

1230

1218

1219

1219

1225(3)

O6-C1

214

1514

2614

1014

1614

151418(3)

C7-C

813

4913

5013

4813

4813

491329(4)

C8-C

914

5914

4914

5314

5914

591431(4)

C11-C

1215

3415

3015

4315

3415

331511(4)

Bond

angle

s(∘ )

C10-N1-C

71213

151213

28120132

1212

841212

661212(2)

C10-N1-C

11117662

11819

4118

819

118043

117666

1199(2)

C7-N

1-C11

120947

120473

120966

120457

120997

1189(2)

C10-N2-C9

128872

128384

130159

1290

67128910

1282(2)

C8-C

7-N1

122075

1216

79123498

122288

122084

1213(2)

C7-C

8-F3

120673

120775

120968

120711

120725

1206(2)

C7-C

8-C9

1217

701219

411212

671216

11121742

1225(2)

F3-C

8-C9

117557

117281

11776

5117667

11753

31169(2)

O5-C9

-N2

1218

741218

501218

631219

091218

651208(2)

O5-C9

-C8

126769

126316

1277

08126747

126814

1273(2)

N2-C9

-C8

111357

111833

110428

111341

111319

1119(2)

O4-C1

0-N2

122497

1219

7612240

4122560

122546

1216(2)

O4-C1

0-N1

122957

123204

123087

123128

122909

1234(2)

N2-C1

0-N1

114543

114820

114509

11431

1114

543

1149(2)

N1-C

11-C1

2113

368

11332

8115

139

113407

113723

1115(2)

O6-C1

2-C1

1113

637

113499

114512

113704

113940

1119(2)


0 100 200 300 400 500 600 700 800 900 1000350375400425450475500525550575600

Temperature (K)

（0 Ｇ

(KJm

ol)

(a)

0 100 200 300 400 500 600 700 800 900 1000

050

100150200250300350400

Temperature (K)

0 Ｇ

(KJm

ol)

minus50

minus100

minus150

minus200

(b)

0 100 200 300 400 500 600 700 800 900 1000250300350400450500550600650700750

Temperature (K)

３0 Ｇ

(KJm

ol)

(c)

Figure 2 Correlation graphics of standard enthalpy H0m Gibbs free energy G0m and entropy S0m with temperatures of the studied molecule

(50minus950 K)

S0m = minus000021T2 + 073125T + 2273794(R2 = 099960)

(5)

These equations have strong correlations with the computedthermodynamic properties Thereby the values of the stan-dard thermodynamic properties H0m G

0m and S0m of the

studied molecule can be predicted at any temperature withthese correlation equations and will be helpful for furtherstudies

The two-layered ONIOMmethod has been used to studythe confinement of the studied molecule inside cappednanotubes SWCNT(120) SWCNT(140) and SWCNT(160)In this work the ONIOMmethod is implemented by treatingthe full system at the low level of theory (a molecularmechanics method) and the interesting part of the systemat high level of theory (a quantum mechanics method) Theenthalpy change HT and the change of Gibbs free energyGT for the confinement reaction between the studiedmolecule and the nanotubes were estimated on the basis ofthe confinement energy found in the literature [34 40 41]The entropy change was derived from HT and GT Theenthalpy change HT the entropy change ST the changeof Gibbs free energy GT and the stability constant log K

for the confinement reaction leading to the optimized hybridnanostructures are reported in Supplementary Material S2As illustrated in Figure 3(a) the HT values are negativeand increase at any temperature from 100 to 900 K Hencethe formation of optimized hybrid nanostructures is anexothermic process The thermodynamic quantity ST pro-vides information about the order or disorder of optimizedhybrid nanostructures The ST values are negative at anytemperature from 100 to 900 K Thus the formation ofoptimized hybrid nanostructures is done in an ordered wayHowever as illustrated in Figure 3(b) a reduction of thedegree of organization of hybrid nanostructures is done withthe increasing temperature because the ST values increaseAs shown in Figure 3(c) the GT values increase in the rangeof 100-900 K In addition the GT values under 900 K arenegative (see Supplementary Material S2) which implies thatthe confinement of the studied molecule inside the hollowspace of capped nanotubes SWCNT(120) SWCNT(140)and SWCNT(160) is possible Thus the formation processof optimized hybrid nanostructures is spontaneous andthermodynamically favorable for temperatures under 900 KAs shown in Figure 3(d) the stability constant log K valuesdecrease with the increasing temperature This implies thatthe interaction between the confined molecule and each


100 200 300 400 500 600 700 800 900Temperature (K)

SWCNT(120)SWCNT(140)SWCNT(160)

minus40

minus38

minus36

minus34

minus32

minus30

minus28

minus42

Δ（

４(K

calm

ol)

(a)

100 200 300 400 500 600 700 800 900Temperature (K)


minus40

minus35

minus25

minus30

minus45

Δ３４

(cal

mol

K)

(b)

100 200 300 400 500 600 700 800 900

0

Temperature (K)


minus40

minus30

minus20

minus10

Δ

４(K

calm

ol)

(c)

100 200 300 400 500 600 700 800 9000

005

01

015

02

Temperature (K)

LogK


(d)

Figure 3 Plots of enthalpy change change ofGibbs free energy entropy change and stability constant against different temperatures (100minus900K) of the optimized hybrid nanostructures

capped nanotube decreases with the increasing temperatureAt low temperatures the interaction between the confinedmolecule and the nanotube is relatively weak

According to the thermodynamic properties and thestability constant computed the confinement of the stud-ied molecule inside capped nanotubes SWCNT(120)SWCNT(140) and SWCNT(160) is possible and the for-mation of optimized hybrid nanostructures is thermody-namically favorable

33 Vibrational Analysis of the Studied Molecule in Gas Phaseand Aqueous Solution Vibrational results are useful to bettercharacterize the studied molecule The quantities of interestin vibrational spectra are frequencies and intensities ThePCM model has been extended to vibrational studies [42]In aqueous solution the reaction field of water perturbsthe molecular potential energy surface (PES) and induceschanges of vibrational frequencies The vibrational frequen-cies IR intensities Raman activities and assignments ofstrong vibrational modes of the studied molecule in gas phaseand aqueous solution are reported in Table 2Most modes are

not pure but contain significant contributions of othermodesThe IR intensity and Raman activity spectra are shown inFigure 4

The solvation of the studied molecule produces greatershifts between the computed values in gas phase and aqueoussolution of IR intensities andRaman activitiesThemaximumIR intensities are 717354 and 1468833 Kmmol and areobserved in gas phase and aqueous solution at 1762630 and1707784 cmminus1 respectively Similarly the maximum Ramanactivities are 202427 and 368806 A4AMU and are observedin gas phase and aqueous solution at 3000562 and 3031451cmminus1 respectively Identical vibrational modes contribute tothe maximum IR intensities and Raman activities in gasphase and aqueous solution but with different intensitiesThe stretching vibrational mode of the bond C10=O andthe bending vibrational mode of angles formed with theN2minusH bond in the plane of the pyrimidine ring constitutetwo contributions to maximum IR intensities of the studiedmolecule in gas phase and aqueous solution The symmetricstretching vibrational modes of the minusCH2 group at positionC12 contribute to maximum Raman activities of the studied

8 Advances in Condensed Matter PhysicsTa

ble2Vibrationalfrequ

ency

(cmminus1)IR

intensity

(Kmm

ol)Ra

man

activ

ity(A4A

MU)andassig

nmentsof

thestu

died

moleculeat

B3LY

P6-31+G

(d)levelin

gasp

hase

andaqueou

ssolutio

nGas

phase

Aqueou

ssolution

ASSIG

NMEN

TSab

Frequency

IRintensity

Raman

activ

ityFrequency

IRIntensity

Raman

activ

ity3693369

69061

44508

3705977

87657

9819

2](06minus

H)

3586430

75248

74241

3577938

115905

1495

67](N2minus

H)

3238231

2895

77440

3251219

6661

182559

](C7minus

H)

3141099

6603

4217

33160

495

8380

10664

1] a

s(CH2C11

andC12)

3084940

3319

7113

127

3111124

43204

166701

] s(C

H2C11)+]

as(C

H2C12)

308112

423687

97655

3104

464

21819

312681

] s(C

H2C11)+]

as(C

H2C12)

3000

562

7415

1202427

3031451

86618

368806

] s(C

H2C12)

178916

9538145

9916

21740

087

4217

501273

85] (C=0C9a

ndC10 )+120575(N2minus

H)

1762630

7173

545220

1707784

1468833

235994

] (C10=O)+120575(N2minus

H)

1711453

1010

795119

7169917

1818283

54809

] (C7=

C8)+120575(C7minus

H)

1529037

1166

9056

1519870

1880

16642

120575(CH2C12

sciss

oring)

1500

104

20636

1317

81496912

43736

27878

120575(CH2C11

sciss

oring)

1482282

55577

3273

1489073

93803

1353

0](r

ingCminusC

andCminusN

strechting)+120574(CH2C11

twisting)

144819

045498

9248

1443952

60681

26451

120575 (O6minus

H)+120574(C

H2C12

overtone)

1427302

23576

7779

1427587

30543

20827

120575 (N2minus

H)+120574(C

H2C12

overtone)

1421510

3616

1511

1423682

23509

6940

120575 (N2minus

HC7minus

H)+120574(C

H2C11

overtone)

1390505

118205

7611

138718

1119

856

11122

120574(CminusHC11

andC12)+120575(O6minus

H)

1380598

3819

640

217

1380309

114269

1316

49120575 (O6minus

HC7minus

H )+120574(C

H2C11

twisting)

1347554

8316

479

091349457

1297

4913904

120575 (O6minus

HC7minus

HN2minus

H)+120574(CminusHC11

andC12)

1281458

4432

317485

1284076

103003

28210

120574(CH2C12

twisting)+120574(CminusHC11 )+120575(C7minusH)

1256870

106831

7770

1240

649

71580

4513

9] (C8minus

FN2minus

C10 )+120575(C7minusH)+120574(C

H2C12

twisting)

1225483

75439

2778

1231243

282155

6081

120574(CH2C11

and

C12t

wisting)+120575(O6minus

HC7minus

HN2minus

H)

11712

7571265

6885

1178572

74246

37119

](ringCminusN

strechting)+120575(O6minus

HC7minus

HN2minus


andC12)

1152566

18908

10654

1144897

77474

17510

] (C11minusN)+120575 (O6minus

HC7minus

H)+120574 (CminusHC11 )

111400

040

616

3788

1092868

41455

9179

] (C12minusO)+120575 (C7minus

H)

1078303

39558

0562

1065832

1210

3817

64120575 (O6minus

H)+120588(C

H2C11

and

C12)

950975

14994

4003

9574

2426819

6760

] (C11minusC12 )+120575(N2minus

HC7minus

H)

9019

4924808

3319

926124

3339

48721

120574(C7minus

H)

888823

16915

2971

888838

38112

6208

120575 (N2minus

HC7minus

H)+120588(

CH2C11

and

C12)+](C11minus

C12 )

856699

1215

76746

85646

428472

12028

120575 (N2minus

H)+120588(

CH2C11)+](C11minus

C12 )

7775

9711367

16247

782228

10639

48556

120575(rin

gCNC

NCN

bend

ing)

7518

940787

0694

752374

0591

2834

120574(ringO4N1N2C10

O5N2C8C9o

utof

planedeform

ation)

7412

8068559

0783

7377

5395416

1452

120574(N2minus

Hw

agging)+120574(r

ingO4N1N2C10

O5N2C8C9o

utof

planedeform

ation)

689145

1874

44013

6897

4533709

6088

120588(CH2C12)+](N1minus

C11 )+120575(rin

gN2C10N1b

ending)

673146

41930

1197

668088

2271

6203

120574(N2minus

Hw

agging)

6673

0512

192541

654352

93406

1226

120588(CH2C11)+120575(rin

gO5C9N2O4C10N2F3C8C7b

ending)

563675

9497

2281

563724

1131

65625

120575(NCC

N1C11C12

bend

ing)+120588(C

H2C12)

5014

5814

9096

74503295

3892

19791

120575(CCOC11C12O6b

ending)+120575(

ringC8C7N1O4C10N2b

ending)

436878

83784

2489

435560

35623

7042

120574(O6minus

Hw

agging)+120575(

ringN2C10N1C11N1C7b

ending)

408328

1272

9013

8440

9922

9849

1315

120574(O6minus

Hw

agging)+120574(

ringC8C7N1C10

outo

fplanedeform

ation)

alim

itedto

thedescrip

tionof

stron

gvibrationalm

odes

ofthestu

died

moleculeandtherepo

rted

vibrationalm

odes

arethoseof

thestu

died

moleculein

gasp

hase

althou

ghmanydescrip

tions

areidenticalin

the

twomedia(in

gasa

ndwater)

b]] sand

] asstr

etching(sim

plesymmetric

and

asym

metric

)120575inplaneb

ending

(sim

plesciss

oring)120574out

ofplaneb

ending

(twistingovertonew

agging

deformation)120588

rocking


0 500 1000 1500 2000 2500 3000 3500 4000

0

500

1000

1500

2000

2500

IR In

tens

ity (K

mm

ol)

Gas phaseAqueous solution

0 500 1000 1500 2000 2500 3000 3500 40000

50

100

150

200

250

300

350

400

450

500


Frequency (＝Ｇ-1) Frequency (＝Ｇ-1)

Ram

an A

ctiv

ity (

4A

MU

)

Figure 4 Vibrational IR and Raman spectra of the studied molecule in gas phase and aqueous solution obtained by DFT simulation

molecule in gas phase and aqueous solution The first threemaximum unscaled vibrational frequencies are found at3693369 3586430 and 3238231 cmminus1 in gas phase and3705977 3577938 and 3251219 cmminus1 in aqueous solutionand correspond to the OminusH stretching vibration N2minusHstretching vibration and C7minusH stretching vibration respec-tively The scaling factor 095 is appropriated to computevibrational frequencies at B3LYP6minus31+G level [43] Themaximum vibrational frequencies found with the scalingfactor 095 are 3508701 3407109 and 3076319 cmminus1 in gasphase and 3520678 3399041 and 3088658 cmminus1 in aqueoussolution respectively The maximum vibrational modes ofthe studied molecule have been observed experimentally at3520 3410 and 2994 cmminus1 [4]The OminusH stretching vibrationusually occurs in the region 3300minus3600 cmminus1 [44] Thevibrational stretching modes N2minusH and C7minusH have beenexperimentally observed in the molecule 5-FU at 2992 and2815 cmminus1 [4] and theoretically observed without scalingfactor with the 3P866minus31G(dp) level at 3640 and 3258 cmminus1[2] respectively In the uracil molecule the N2minusH and C7minusHvibrational modes have been experimentally observed at 3160and 3090 cmminus1 [1] and theoretically observed without scalingfactor with the B3LYP6minus311++G(dp) basis at 3597 and 3244cmminus1 [1] respectively Thereby with the scaling factor 095the computed vibrational frequencies at B3LYP6minus31+G(d)are in good agreement with the experimental IR frequenciesvalues [4]

34 Nonlinear and Electronic Properties Gibbs Free Energy ofSolvation and Quantum Molecular Descriptors of the StudiedMolecule Thenonlinear optical (NLO) properties of organicmolecules are extensively investigated with density function-als [45] The values of the computed NLO properties aregathered in Table 3The following relations have been used toconvert the mean polarizability (120572m) and the static first-order

Table 3 Calculated dipole moment 120583119905119900119905(D) mean polarizability120572m(A3) mean first-order hyperpolarizability 120573m(times10minus30cm5esu)and HOMO-LUMO energy gap Eg(eV) of the studied molecule ingas phase and aqueous solution at STP (T=29815 K)

Gas phase Aqueous solutionCPCM

Properties B3LYP6minus31+G(d) B3LYP6minus31+G(d)120583tot 5117 7292120572m 14298 18725120573m 1487 1576Eg 5167 5165

hyperpolarizability (120573m) in electrostatic units (esu) 1 au of120572 = 0148x10minus24 esu and 1 au of 120573 = 8639x10minus33 esuIn aqueous solution the values of 120583tot 120572m and 120573m increaseWhen the studied molecule is solvated the reaction field ofwatermodifies the nonlinear responses The calculated dipolemoment is 5117 D in gas phase The computed 120583tot valueof the urea molecule is 4590D with the B3LYP6minus31+G(d)method Gester et al [46] have reported a 120583tot value of 393D in gas phase and 591 D in aqueous solution for the 5-FUmolecule The polarizability tensor (120572ij) is dominated by thediagonal components and the highest value is obtained for thecomponent120572xx In this direction the found value is 19249 A3in gas phase and 25071 A3 in aqueous solution The 120572mvalue of the studied molecule is greater than that of urea(120572urea = 4181 A3 at B3LYP6minus31+G(d) level) Basis sets haveeffects on the hyperpolarizability Fernando et al [47] haveshown that the inclusion of diffuse functions into basis sets iscrucial to obtain accurate results of the hyperpolarizabilityTherefore diffuse basis sets give acceptable values of thehyperpolarizability The urea molecule is a well-known NLOmaterial and is widely used to predict good NLO material


HOMO (-7122 eV) LUMO (-1955 eV)

Figure 5 HOMO and LUMO molecular orbitals of the studiedmolecule in gas phase

on the basis of the static first-order hyperpolarizability The120573m value of urea computed at the B3LYP6minus31+G(d) level is0526 times 10minus30cm5esu This value is slightly lower than thevalue reported in the literature at B3LYP6minus31++G(dp) level(120573m = 0770times10minus30cm5esu) [48]The120573m value of the studiedmolecule is 1487 times 10minus30cm5esu which is theoretically282 times greater than that of urea at B3LYP6minus31+G(d)level These results show that the studied molecule is a goodcandidate as second-order NLOmaterial

The analysis of electronic properties of organic moleculesis usually related to frontier orbitals [17] The HOMO andLUMO orbitals and the density of states (DOS) plot of thestudied molecule are shown in Figures 5 and 6 The LUMOorbital is mainly localized on the pyrimidine ring whilethe HOMO orbital is localized on the whole molecule TheHOMO and LUMO values are minus7122 eV and minus1955 eV in gasphase and minus6947 eV and minus1782 eV in aqueous solution Thesolvation modifies slightly the band structure of the studiedmolecule The results of the energy gap (Eg) gathered inTable 3 show that the solvation decreases slightly the Eg valuewhen the studied molecule is moved from the gas phase toaqueous solution The large Eg values found refer to highexcitation energies for many excited states and suggest a goodstability for the studied therapeutic molecule

Pienko et al [49] have reported in the literature that thesolubility is a crucial parameter for bioavailability predictionof therapeutic molecule The Gibbs free energy of solva-tion (Gsol) is a physicochemical parameter related to thesolubility which can be derived from quantum mechanicalcalculations From thermodynamic consideration negativevalues of Gsol mean that the process of solvation is spon-taneous The more negative the Gsol value the higher thedegree of solubility The computed Gsol value of the studiedmolecule is minus18524 Kcalmol Therefore the dissolution inwater of the studied molecule is spontaneous The computedGsol value of the 5-FU molecule is minus15950 Kcalmol withthe CPCMB3LYP6minus31+G(d) method This shows that thestudied molecule is more soluble than the 5-FU moleculeThe increase in the degree of solubility in water of thestudiedmolecule in comparison to 5-FUmolecule is probablyinduced by the presence of the 1-(2-hydroxyethyl) fragment

Table 4 Quantummolecular descriptors of the studied molecule ingas phase and aqueous solution

Gas phase Aqueous solutionQuantum molecular CPCMDescriptors B3LYP6minus31+G(d) B3LYP6minus31+G(d)EA (eV) 1955 1782IP (eV) 7122 6947120594 (eV) 4539 4365120583 (eV) minus4539 minus4365120578 (eV) 2584 2583S (eVminus1) 0387 0387120596 (eV) 3986 3688

Recently Zafar et al [50] have estimated the range of Gibbsfree energy of solvation in drug design they have reportedthat the Gsol value of quality drug candidates should be lessthan minus12 Kcalmol the Gsol value of the studied molecule ismuch less than minus12 KcalmolTherefore the studied moleculeis a promising quality drug candidate

Table 4 shows the calculated quantum molecular descrip-tors of the studied molecule in gas phase and aqueoussolution When the studied molecule is moved from the gasphase to aqueous solution the values of EA IP 120594 120583 120578 and 120596decrease

The computed values of the electron affinity (EA) and theionization potential (IP) of the 5-FU molecule are 1955 and7276 eV with the B3LYP6minus31+G(d) method respectivelyThe IP value of the studied molecule decreases in comparisonto that of the 5-FU molecule However the EA value doesnot change because the LUMO orbital which is directlyrelated to the electron affinity is localized on the pyrimidinering Furthermore the values of 120594 and 120583 of the 5-FUmolecule are 4615 and minus4615 eV respectively These resultsshow that the reactivity of the studied molecule is improvedbecause its IP value decreases while its 120583 value increasesin comparison to those of the 5-FU molecule The harnessof a molecule refers to its resistance toward deformation inpresence of an electric field Usually a soft molecule has asmall energy gap while a hard molecule has a large energygap The studied molecule is hard because its harness isgreater than its softness This result is in agreement with thelarge energy gap found The computed values of 120578 and S ofthe 5-FU molecule are 2660 eV and 0375 eVminus1 with theB3LYP6minus31+G(d) method respectively The comparison ofthe harness and softness of the studied molecule with thoseof the 5-FU molecule indicates that the studied molecule ismore soft and less hard than the 5-FU molecule Schwobel etal [51] have reported a review of experimental and theoreticalmethods of measurement and estimation of electrophilicreactivity It appears that the electrophilicity index is a gooddescriptor to measure the electrophilic reactivity of chemicalcompounds Parthasarathi et al [52] have reported in theliterature a study on the biological activity prediction with theelectrophilicity index Their results show that the biologicalactivity of chemical compounds may be effectively describedwith the electrophilicity index Furthermore Roy et al [53]


0 1 2 3 4 5

0

1

2

3

Energy (eV)

DOS spectrum Occupied orbitalsVirtual orbitals

5167 eV

minus15 minus14 minus13 minus12 minus11 minus10 minus9 minus8 minus7 minus5 minus4 minus3 minus2 minus1minus6

Figure 6 Density of states (DOS) of the studied molecule in gas phase

Figure 7 The total electron density mapped with electrostaticpotential of the studied molecule

have reported research work on the toxicity prediction withthe electrophilicity They showed that the electrophilicity is apromising descriptor for toxicological prediction consideringthe case of aliphatic compounds The 120596 value of the studiedmolecule varies very slightly in comparison to 5-FUmolecule(120596 = 4003 eV with the B3LYP6minus31+G(d) method) Thismolecule is hard electrophile

The sites for nucleophilic and electrophilic reactions havebeen determined with the molecular electrostatic potential(MEP) Figure 7 shows the total electron density surfacemapped with electrostatic potential of the studied moleculePotential increases in the order red lt orange lt yellow ltgreen lt blue Atoms localized in the red regions are negativepotential sites and participate in electrophilic reactions whileatoms localized in the blue regions are positive potential sitesand participate in nucleophilic reactionsTheV(r) values nearthe atoms O5 O6 O4 and F of the studied molecule are

minus0052 minus0041 minus0033 and minus0022 au respectively Thesesites are the most negative potential sites and are involvedin electrophilic reactions The most positive potential sitesare localized near the C7minusH and N2minusH bonds The V(r)values near the C7minusH and N2minusH bonds are 0055 and0052 au respectively These sites are involved in nucleophilicreactionsThese results provide information of sites where thestudied molecule can have intermolecular interactions withother compounds (as a nanotube during the confinementprocess and water during the solvation process) and covalentbonding with toxic proteins in the inhibition process of theiractivities

4 Conclusions

Density functional theory calculations have been performedon the molecule 1-(2-hydroxyethyl)-5-fluorouracil in gasphase and aqueous solution and the ONIOM method hasbeen performed to investigate the possibility of its con-finement inside capped carbon nanotubes SWCNT(120)SWCNT(140) and SWCNT(160) The results found forstructural parameters of the studied molecule are in goodagreement with the X-ray crystallographic data The solva-tion and the confinement inside nanotubes of the studiedmolecule change slightly its molecular geometrical param-eters Correlation equations have been obtained to predictthe standard thermodynamics properties H0m G

0m and S0m

of the studied molecule at any temperatures The analysisof the thermodynamic properties 119867119879 119878119879 and 119866119879 andthe stability constant log119870 leads to the prediction that theconfinement of the studied molecule inside these nanotubesis possible and the formation of optimized hybrid nanostruc-tures is thermodynamically favorable Vibrational analysishas been performed to better characterize the optimized


molecule in gas phase and aqueous solution The solvationof the studied molecule produces greater shifts between thecomputed values in gas phase and aqueous solution of IRintensities and Raman activities The predicted nonlinearproperties of the studied molecule are much greater thanthose of urea The studied molecule is a good candidate assecond-order NLO material The large Eg values found sug-gest a good stability for the studied molecule The calculated119866119904119900119897 values suggest that the studiedmolecule ismore solublethan the 5-FU molecule Frontier molecular orbital (FMO)energies have been employed to study the quantummoleculardescriptors according to Koopmans theorem The solvationdecreases the values of EA IP 120594 120583 120578 and 120596The results of EAand IP show that the studied molecule has the same tendencyto accept electrons as the 5-FU molecule from a donor andits reactivity is higher than that of the 5-FU molecule The 120583value of this fluorouracil derivative confirms that its reactivityis improved in comparison to that of the 5-FUmolecule Thestudied molecule is more soft and less hard than the 5-FUmolecule The 120596 value of the studied molecule changes veryslightly in comparison to that of the 5-FUmolecule We hopethat these results will be helpful for other researches on neworganic materials drugs and hybrid nanostructures

Data Availability

The data used to support the findings of this study areincluded within the article

Conflicts of Interest

The authors declare that there are no conflicts of interest asconcerns this article

Acknowledgments

We are thankful to the Council of Scientific and Indus-trial Research (CSIR) India forfinancial support throughEmeritus Professor scheme (grant no 21(0582)03EMR-II)to Late Prof AN Singh of the Physics Department BahamasHindu University India which enabled him to purchase theGaussian Software We are most grateful to Late EmeritusProf AN Singh for donating this software to one of us DrGeh Wilson Ejuh and to the Materials Science Laboratoryof the University of Yaounde I for enabling us to use theircomputing facilities

Supplementary Materials

The standard enthalpy Gibbs free energy and entropy of thestudied fluorouracil derivative at temperatures in the rangeof 50-950 K are listed in Supplementary Material 1 Theenthalpy change the change of Gibbs free energy the entropychange and stability constant for the confinement reaction ofthe optimized hybrid nanostructures at temperatures in therange of 100minus900 K are listed in Supplementary Material 2associated with this manuscript (Supplementary Materials)

References

[1] J Singh ldquoFT-IR and Raman spectra ab initio and densityfunctional computations of the vibrational spectra moleculargeometries and atomic charges of uracil and 5-methyluracil(thymine)rdquo Spectrochimica Acta Part A Molecular andBiomolecular Spectroscopy vol 137 pp 625ndash640 2015

[2] V K Rastogi V Jain R A Yadav C Singh and M A PalafoxldquoFourier transform Raman spectrum and ab initio and densityfunctional computations of the vibrational spectrummoleculargeometry atomic charges and some molecular properties ofthe anticarcinogenic drug 5-fluorouracilrdquo Journal of RamanSpectroscopy vol 31 no 7 pp 595ndash603

[3] J L Arias ldquoNovel strategies to improve the anticancer action of5-fluorouracil by using drug delivery systemsrdquo Molecules vol13 no 10 pp 2340ndash2369 2008

[4] X Xu G Yao Y Li et al ldquo5-Fluorouracil derivatives from thesponge Phakellia fuscardquo Journal of Natural Products vol 66 no2 pp 285ndash288 2003

[5] R Bagheri M Babazadeh E Vessally M Esrsquohaghi and ABekhradnia ldquoSi-doped phagraphene as a drug carrier foradrucil anti-cancer drug DFT studiesrdquo Inorganic ChemistryCommunications vol 90 pp 8ndash14 2018

[6] S A Siadati K Kula and E Babanezhad ldquoThe possibilityof a two-step oxidation of the surface of C20 fullerene bya single molecule of nitric (V) acid initiate by a rare [2+3]cycloadditionrdquo Chemical Review and Letters vol 2 pp 2ndash62019

[7] R Rostamoghli M Vakili A Banaei E Pourbashir and KJalalierad ldquoApplying the B12N12 nanoparticle as the CO CO2H2O and NH3 sensorrdquo Chemical Review and Letters vol 1 pp31ndash36 2018

[8] E Babanezhad and A Beheshti ldquoThe possibility of selectivesensing of the straight-chain alcohols (including methanol ton-pentanol) by using the C20 fullerene and C18NB nano cagerdquoChemical Review and Letters vol 1 pp 82ndash88 2018

[9] S A Siadati and S Rezazadeh ldquoSwitching behavior of anactuator containing germanium silicon-decorated and normalC20 fullerenerdquo Chemical Review and Letters vol 1 pp 77ndash812018

[10] J M Rabanel V Aoun I Elkin M Mokhtar and P HildgenldquoDrug-loaded nanocarriers passive targeting and crossing ofbiological barriersrdquo CurrentMedicinal Chemistry vol 19 no 19pp 3070ndash3102 2012

[11] K Zare and N Shadmani ldquoComparison of drug deliverysystems nanotube and p- sulphonatocalix[4]arene by densityfunctional theoryrdquo Journal of Nanostructure in Chemistry vol3 pp 72ndash77 2013

[12] A R Harutyunyan B K Pradhan G U Sumanasekera E YKorobko and A A Kuznetsov ldquoCarbon nanotubes for medicalapplicationsrdquo European Cells and Materials vol 3 pp 84ndash872002

[13] S Costa E Borowiak-Palen A Bachmatiuk M H RummeliT Gemming and R J Kalenczuk ldquoFilling of carbon nanotubesfor bio-applicationsrdquo Physica Status Solidi (b) ndash Basic Solid StatePhysics vol 244 no 11 pp 4315ndash4318 2007

[14] M Robinson I Suarez-Martinez and N A Marks ldquoGen-eralized method for constructing the atomic coordinates ofnanotube capsrdquo Physical Review B Condensed Matter andMaterials Physics vol 87 no 15 pp 1ndash8 2013

[15] F Jensen Introduction to Computational Chemistry JohnWileyamp Sons 2017


[16] F Sen M Dincer A Cukurovali and I Yilmaz ldquoN-[4-(3-methyl-3-mesityl-cyclobutyl)-thiazol-2-yl]-succinamicacid X-ray structure spectroscopic characterization andquantum chemical computational studiesrdquo Journal of MolecularStructure vol 1046 pp 1ndash8 2013

[17] GW Ejuh N Samuel T N Fridolin andN JMarie ldquoCompu-tational determination of the electronic and nonlinear opticalproperties of the molecules 2-(4-aminophenyl) quinoline 4-(4 aminophenyl) quinoline anthracene anthraquinone andphenanthrenerdquoMaterials Letters vol 178 pp 221ndash226 2016

[18] Y J Dappe ldquoEncapsulation of organic molecules in carbonnanotubes role of the van der waals interactionsrdquo Journal ofPhysics D Applied Physics vol 47 no 8 pp 1ndash16 2014

[19] T Vreven K S Byun I Komaromi et al ldquoCombining quantummechanics methods with molecular mechanics methods inONIOMrdquo Journal of Chemical Theory and Computation vol 2no 3 pp 815ndash826 2006

[20] L W Chung W M Sameera R Ramozzi et al ldquoThe ONIOMmethod and its applicationsrdquo Chemical Reviews vol 115 no 12pp 5678ndash5796 2015

[21] G Garcıa I Ciofini M Fernandez-Gomez and C AdamoldquoConfinement effects on UVndashvisible absorption spectra 120573-carotene inside carbon nanotube as a test caserdquo The Journal ofPhysical Chemistry Letters vol 4 no 8 pp 1239ndash1243 2013

[22] A Ahmadi M Kamfiroozi J Beheshtian and N L HadipourldquoThe effect of surface curvature of aluminum nitride nanotubeson the adsorption of NH3rdquo Structural Chemistry vol 22 no 6pp 1261ndash1265 2011

[23] J Prasek J Drbohlavova J Chomoucka et al ldquoMethodsfor carbon nanotubes synthesismdashreviewrdquo Journal of MaterialsChemistry vol 21 no 40 pp 15872ndash15884 2011

[24] B C Satishkumar AGovindaraj JMofokeng G N Subbannaand C N Rao ldquoNovel experiments with carbon nanotubesopening filling closing and functionalizing nanotubesrdquo Journalof Physics B Atomic Molecular and Optical Physics vol 29 no21 pp 4925ndash4934 1996

[25] P M Ajayan T W Ebbesen T Ichihashi S Iijima K Tanigakiand H Hiura ldquoOpening carbon nanotubes with oxygen andimplications for fillingrdquo Nature vol 362 no 6420 pp 522ndash5251993

[26] M Yudasaka K Ajima K Suenaga T Ichihashi A Hashimotoand S Iijima ldquoNano-extraction and nano-condensation forC60 incorporation into single-wall carbon nanotubes in liquidphasesrdquo Chemical Physics Letters vol 380 no 1-2 pp 42ndash462003

[27] Y Ren andG Pastorin ldquoIncorporation of hexamethylmelamineinside capped carbon nanotubesrdquo Advanced Materials vol 20no 11 pp 2031ndash2036 2008

[28] L Wu C Man H Wang et al ldquoPEGylated multi-walledcarbon nanotubes for encapsulation and sustained release ofoxaliplatinrdquo Pharmaceutical Research vol 30 no 2 pp 412ndash423 2013

[29] T A Hilder and J M Hill ldquoEncapsulation of the anticancerdrug cisplatin into nanotubesrdquo in Proceedings of the Interna-tional Conference on Nanoscience and Nanotechnology ICONNrsquo08 pp 109ndash112 Australia 2008

[30] M J Frisch G W Trucks H B Schlegel et al Gaussian 09Revision A02 Gaussian Inc Wallingford CT USA 2009

[31] R Dennington T Keith and J Millam GaussView Version 5Semichem Inc Shawnee Mission Kan USA 2009

[32] A V Marenich C J Cramer and D G Truhlar ldquoUniversalsolvation model based on solute electron density and on acontinuum model of the solvent defined by the bulk dielectricconstant and atomic surface tensionsrdquo The Journal of PhysicalChemistry B vol 113 no 18 pp 6378ndash6396 2009

[33] L X Wang C H YI H T Zou J Xu and W L Xu ldquocis-transisomerization of azobenzene confined inside an armchair (8 8)single-walled carbon nanotuberdquo Acta Physico-Chimica Sinicavol 26 pp 149ndash154 2010

[34] L Wang C Yi H Zou J Xu andW Xu ldquoOn the isomerizationand dissociation of nitramide encapsulated inside an armchair(55) single-walled carbon nanotuberdquoMaterials Chemistry andPhysics vol 127 no 1-2 pp 232ndash238 2011

[35] S F Boys and F Bernardi ldquoThe calculation of small molecularinteractions by the differences of separate total energies Someprocedures with reduced errorsrdquoMolecular Physics vol 19 no4 pp 553ndash566 1970

[36] R A Yossa Kamsi G W Ejuh F Tchoffo P Mkounga and J BNdjaka ldquoElectronic structure spectroscopic (IR Raman UV-Vis NMR) optoelectronic and NLO properties investigationsof rubescin E(C31H36O7) molecule in gas phase and chloro-form solution using Ab initio and DFT methodsrdquo Advancesin Condensed Matter Physics vol 2019 Article ID 4246810 22pages 2019

[37] N M Orsquoboyle A L Tenderholt and K M Langner ldquoccliba library for package-independent computational chemistryalgorithmsrdquo Journal of Computational Chemistry vol 29 no 5pp 839ndash845 2008

[38] Y Tadjouteu Assatse G Ejuh F Tchoffo and J Ndjaka ldquoDFTstudies of nanomaterials designed by the functionalizationof modified carboxylated carbon nanotubes with biguanidederivatives for nanomedical nonlinear and electronic applica-tionsrdquo Chinese Journal of Physics vol 58 pp 253ndash262 2019

[39] P Politzer and J S Murray ldquoThe fundamental nature and role ofthe electrostatic potential in atoms and moleculesrdquo TheoreticalChemistry Accounts vol 108 pp 134ndash142 2002

[40] B Trzaskowski and L Adamowicz ldquoChloromethane anddichloromethane decompositions inside nanotubes as modelsof reactions in confined spacerdquoTheoretical Chemistry Accountsvol 124 no 1-2 pp 95ndash103 2009

[41] L Wang C Yi H Zou J Xu and W Xu ldquoRearrangementand thermal decomposition of nitromethane confined insidean armchair (55) single-walled carbon nanotuberdquo ChemicalPhysics vol 367 no 2-3 pp 120ndash126 2010

[42] B Mennucci and R Cammi Continuum Solvation Models inChemical Physics From Theory to Applications John Wiley ampSons 2007

[43] M s Boobalan D Tamilvendan M Amaladasan S Rama-lingam G Venkatesa Prabhu and M Bououdina ldquoVibrationalspectra and electronic structure of 3-((1H-pyrrol-1-yl) methyl)naphthalen-2-olndashA computational insight on antioxidant activeMannich baserdquo Journal ofMolecular Structure vol 1081 pp 159ndash174 2015

[44] M Szafran A Komasa and Z Dega-Szafran ldquoSpectro-scopic and theoretical studies of bis(dimethylphenyl betaine)hydrochloride monohydraterdquo Vibrational Spectroscopy vol 79pp 16ndash23 2015

[45] B Champagne E A Perpete D Jacquemin et al ldquoAssessmentof conventional density functional schemes for computing thedipole moment and (hyper) polarizabilities of pushminus pull 120587-conjugated systemsrdquo The Journal of Physical Chemistry A vol104 no 20 pp 4755ndash4763 2000


[46] R M Gester C Bistafa H C Georg K Coutinho and SCanuto ldquoTheoretically describing the 17O magnetic shieldingconstant of biomolecular systems uracil and 5-fluorouracil inwater environmentrdquo Theoretical Chemistry Accounts vol 133no 1424 pp 1ndash8 2014

[47] F D Vila D A Strubbe Y Takimoto et al ldquoBasis set effectson the hyperpolarizability of CHCl3 Gaussian-type orbitalsnumerical basis sets and real-space gridsrdquo The Journal ofChemical Physics vol 133 no 3 pp 1ndash23 2010

[48] H Tanak ldquoldquoMolecular structure spectroscopic (FT-IR andUV-Vis) and DFT quantum-chemical studies on 2-[(2 4-dimethylphenyl) iminomethyl]-6-methylphenolrdquo MolecularPhysics vol 112 no 11 pp 1553ndash1565 2014

[49] T Pienko M Grudzien P P Taciak and A P MazurekldquoCytisine basicity solvation log P and log D theoreticaldetermination as tool for bioavailability predictionrdquo Journal ofMolecular Graphics and Modelling vol 63 pp 15ndash21 2016

[50] A Zafar and J Reynisson ldquoHydration free energy as amoleculardescriptor in drug design a feasibility studyrdquo Molecular Infor-matics vol 35 no 5 pp 207ndash214 2016

[51] J A Schwobel Y K Koleva S J Enoch et al ldquoMeasurement andestimation of electrophilic reactivity for predictive toxicologyrdquoChemical Reviews vol 111 no 4 pp 2562ndash2596 2011

[52] R Parthasarathi V Subramanian D R Roy and P K ChattarajldquoElectrophilicity index as a possible descriptor of biologicalactivityrdquo Bioorganic amp Medicinal Chemistry vol 12 no 21 pp5533ndash5543 2004

[53] D R Roy R Parthasarathi B Maiti V Subramanian and P KChattaraj ldquoElectrophilicity as a possible descriptor for toxicitypredictionrdquo Bioorganic amp Medicinal Chemistry vol 13 no 10pp 3405ndash3412 2005

Hindawiwwwhindawicom Volume 2018

Active and Passive Electronic Components


Shock and Vibration


High Energy PhysicsAdvances in

Hindawi Publishing Corporation httpwwwhindawicom Volume 2013Hindawiwwwhindawicom

The Scientific World Journal

Volume 2018

Acoustics and VibrationAdvances in



Advances in Condensed Matter Physics

OpticsInternational Journal of



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Antennas andPropagation

International Journal of




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Hindawiwwwhindawicom

Volume 2018

Applied Bionics and BiomechanicsHindawiwwwhindawicom Volume 2018

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Journal of

Chemistry


Advances inPhysical Chemistry


RotatingMachinery



Journal ofEngineeringVolume 2018

Submit your manuscripts atwwwhindawicom


thus offering the possibility of using them in gene therapyZare et al [11] have reported a research work on thecomparison of drug delivery systems They have shown thatcarbon nanotubes deliver the 5-FU molecule better than thep-sulfonatocalix-[4]-arene Carbon nanotubes have a greatpotential to carry molecules Many studies on medical andbiomedical applications [12 13] of carbon nanotubes havebeen reported in the literature Robinson et al [14] havedeveloped a generalized numerical method for generating theatomic coordinates of nanotube caps

Many computational methods [15] have been developedto investigate the properties of molecules Density functionaltheory (DFT) is greatly used in molecular computationalstudy This computational method reproduces very well theexperimental properties of molecules such as geometricalstructures vibrational properties and nonlinear and elec-tronic properties [16 17] Recently it has been reported thatthe van der Waals interactions play a major role in theencapsulation of molecules inside carbon nanotubes [18]Thevan der Waals interactions can be taken into considerationin the modeling of hybrid nanostructures using the quantummechanics (QM)molecular mechanics (MM) calculationsespecially the ONIOM method The ONIOM method [19]has proved to be a powerful tool in combining quantummechanics and molecular mechanics calculations Chung etal [20] have reported a review on theONIOMmethod and itsapplications In their review many theoretical investigationsusing ONIOM methods on the encapsulation of moleculesinside carbon nanotubes and other nanostructures have beenreported In particular Garcia et al [21] have studied theconfinement of 120573-carotene inside carbon nanotubes usingan ONIOM method Ahmadi et al [22] have studied theadsorption of ammonia molecules inside aluminum nitridenanotubes using an ONIOM method To experimentallyencapsulate a drug into a capped carbon nanotube thefirst step is to synthesize the carbon nanotube [23] As thesynthesized nanotubes are usually closed by domes at leastone end must be opened before incorporation of the drugThe opening of the nanotube can be done by chemicaloxidation [24] or thermal oxidation [25] Yudasaka et al [26]have developed two different methods called nanoextractionand nanocondensation to incorporate guest molecules intosingle-walled carbon nanotubes in liquid phases Ren et al[27] have applied the nanoextraction method to incorpo-rate the antitumor agent hexamethylmelamine into carbonnanotubes Recently Wu et al [28] have also used thenanoextraction method to incorporate the antitumor agentoxaliplatin into multiwalled carbon nanotubes Satishkumaret al [24] have reported experimental methods for closingcarbon nanotubes They have experimentally shown thatuncapped nanotubes can be closed by the reaction at hightemperature with benzene vapour in a reducing atmosphereof hydrogen and argon

To the best of our knowledge this is the first theoreticalstudy on themolecule 1-(2-hydroxyethyl)-5-fluorouracil pub-lished The aim of this work is to investigate the properties ofthe molecule 1-(2-hydroxyethyl)-5-fluorouracil in gas phaseand aqueous solution Furthermore the changes occurring inthe molecular geometrical structure and the thermodynamic

stability when it is confined inside the hollow space of cappednanotubes SWCNT(120) SWCNT(140) and SWCNT(160)by considering mainly the van der Waals interaction havebeen investigated This study is performed to predict theencapsulation of this molecule into carbon nanotubes thelong-term objective is to perform a targeted delivery of thismolecule in cancer cells following the model proposed byHilder et al [29] In this study the molecular structureanalysis of the studied molecule has been performed ingas phase and aqueous solution by a DFT method andinside the nanotube cavity by anONIOM(DFTMM)methodThe thermodynamic properties of the studied moleculeand the thermodynamic stability study of the optimizedhybrid nanostructures have been investigated at differenttemperatures The vibrational analysis the nonlinear andelectronic properties the Gibbs free energy of solvation andthe quantum molecular descriptors of the studied moleculehave been investigated in gas phase and aqueous solution

2 Computational Methodology

Density functional theory (DFT) was performed for thecalculations of properties of the studied molecule in gasphase and aqueous solution while the ONIOM(DFTMM)method was performed to study the hybrid nanostructuresThe hybrid nanostructures were obtained by the confinementof the studied molecule inside the nanotube cavities Weused capped nanotubes SWCNT(120) SWCNT(140) andSWCNT(160) of 336 428 and 488 carbon atoms respec-tively The diameters of these nanotubes are 9402 A 10968A and 12536 AThese nanotubes were chosen to point up thediameter range of carbon nanotubes that allow the studiedmolecule to be confined without any significant moleculargeometry alterationThe uncapped nanotubes SWCNT(120)SWCNT(140) and SWCNT(160) have a finite length of 1739A and they have 204 238 and 272 carbon atoms respectivelyEach cap of these nanotubes was formed with pentagonaldefects The 2D projections of the capped nanotubes areshown in Figure 1(a) The full geometry optimizations wereperformed on the studied molecule and the hybrid nanos-tructures using Gaussian 09 W program [30] The results ofsimulations were visualized by GaussView 5 program [31]We used the functional B3LYP with the 6minus31+G(d) basis setto implement DFT calculations The polarizable continuummodel with a conductor solvent model (CPCM) was appliedto account for solvation effects In our calculations water(dielectric constant (120576) of 784)was used as solvatingmediumThe Gibbs free energy of solvation was calculated by takingthe difference between the total electronic energy in waterafter polarized continuum model (PCM) corrections usingthe SMD continuum model [32] and the total electronicenergy in gas phase

The inclusion of vanderWaals (vdW) interactions [18] foran accurate description of the molecular structure of nanos-tructures designed by encapsulation of molecule inside thehollow space of nanotube is indispensable The combinationof DFT with the united force field (UFF) has been widelyused [33 34] The noncovalent interactions were applied



(a) (b)


(c)









V (r) = sumA


120588 (r1015840)1003816100381610038161003816r1015840 minus r1003816100381610038161003816

dr1015840 (2)







0m


H0m = 000017T2 + 007498T + 36419947(R2 = 099951)

(3)


(4)


Table1Molecular

geom

etric

alparameterso

fthe

studied

moleculeingasp

haseaqu

eous

solutio

nandtheh

ollowspaceo

fthe

nano

tubesS

WCN

T(120)SW

CNT(140)andSW

CNT(160)

Gas

Phase

Aqueou

ssolutio

nInsid

ecapp

ed-SWCN

T(120)

Insid

ecapp

ed-SWCN

T(140)

Insid

ecapp

ed-SWCN

T(160)

Experim

ental

[4]

B3LY

P6minus

31+G

(d)

B3LY

P6minus

31+G

(d)

ONIO

M(B3LYP

6minus31

+G(d)U

FF)

ONIO

M(B3LYP

6minus31

+G(d)U

FF)

ONIO

M(B3LYP

6minus31

+G(d)U

FF)

Bond

lengths

(A)

N1-C

1013

9213

8813

8213

9313

911373(3)

N1-C

713

8213

7713

8113

8113

821376(3)

N1-C

1114

7114

7614

8114

7014

721479(3)

N2-C1

013

8413

8513

8013

8513

841374(3)

N2-C9

1407

1397

1405

1407

1408

1385(3)

F3-C

813

4513

5213

4313

4513

441355(3)

O4-C1

012

2812

3112

2812

2712

281228(3)

O5-C9

1219

1230

1218

1219

1219

1225(3)

O6-C1

214

1514

2614

1014

1614

151418(3)

C7-C

813

4913

5013

4813

4813

491329(4)

C8-C

914

5914

4914

5314

5914

591431(4)

C11-C

1215

3415

3015

4315

3415

331511(4)

Bond

angle

s(∘ )

C10-N1-C

71213

151213

28120132

1212

841212

661212(2)

C10-N1-C

11117662

11819

4118

819

118043

117666

1199(2)

C7-N

1-C11

120947

120473

120966

120457

120997

1189(2)

C10-N2-C9

128872

128384

130159

1290

67128910

1282(2)

C8-C

7-N1

122075

1216

79123498

122288

122084

1213(2)

C7-C

8-F3

120673

120775

120968

120711

120725

1206(2)

C7-C

8-C9

1217

701219

411212

671216

11121742

1225(2)

F3-C

8-C9

117557

117281

11776

5117667

11753

31169(2)

O5-C9

-N2

1218

741218

501218

631219

091218

651208(2)

O5-C9

-C8

126769

126316

1277

08126747

126814

1273(2)

N2-C9

-C8

111357

111833

110428

111341

111319

1119(2)

O4-C1

0-N2

122497

1219

7612240

4122560

122546

1216(2)

O4-C1

0-N1

122957

123204

123087

123128

122909

1234(2)

N2-C1

0-N1

114543

114820

114509

11431

1114

543

1149(2)

N1-C

11-C1

2113

368

11332

8115

139

113407

113723

1115(2)

O6-C1

2-C1

1113

637

113499

114512

113704

113940

1119(2)


0 100 200 300 400 500 600 700 800 900 1000350375400425450475500525550575600

Temperature (K)

（0 Ｇ

(KJm

ol)

(a)

0 100 200 300 400 500 600 700 800 900 1000

050

100150200250300350400

Temperature (K)

0 Ｇ

(KJm

ol)

minus50

minus100

minus150

minus200

(b)

0 100 200 300 400 500 600 700 800 900 1000250300350400450500550600650700750

Temperature (K)

３0 Ｇ

(KJm

ol)

(c)


(50minus950 K)

S0m = minus000021T2 + 073125T + 2273794(R2 = 099960)

(5)


0m and S0m of the





100 200 300 400 500 600 700 800 900Temperature (K)


minus40

minus38

minus36

minus34

minus32

minus30

minus28

minus42

Δ（

４(K

calm

ol)

(a)

100 200 300 400 500 600 700 800 900Temperature (K)


minus40

minus35

minus25

minus30

minus45

Δ３４

(cal

mol

K)

(b)

100 200 300 400 500 600 700 800 900

0

Temperature (K)


minus40

minus30

minus20

minus10

Δ

４(K

calm

ol)

(c)

100 200 300 400 500 600 700 800 9000

005

01

015

02

Temperature (K)

LogK


(d)









ency

(cmminus1)IR

intensity

(Kmm

ol)Ra

man

activ

ity(A4A

MU)andassig

nmentsof

thestu

died

moleculeat

B3LY

P6-31+G

(d)levelin

gasp

hase

andaqueou

ssolutio

nGas

phase

Aqueou

ssolution

ASSIG

NMEN

TSab

Frequency

IRintensity

Raman

activ

ityFrequency

IRIntensity

Raman

activ

ity3693369

69061

44508

3705977

87657

9819

2](06minus

H)

3586430

75248

74241

3577938

115905

1495

67](N2minus

H)

3238231

2895

77440

3251219

6661

182559

](C7minus

H)

3141099

6603

4217

33160

495

8380

10664

1] a

s(CH2C11

andC12)

3084940

3319

7113

127

3111124

43204

166701

] s(C

H2C11)+]

as(C

H2C12)

308112

423687

97655

3104

464

21819

312681

] s(C

H2C11)+]

as(C

H2C12)

3000

562

7415

1202427

3031451

86618

368806

] s(C

H2C12)

178916

9538145

9916

21740

087

4217

501273

85] (C=0C9a


H)

1762630

7173

545220

1707784

1468833

235994

] (C10=O)+120575(N2minus

H)

1711453

1010

795119

7169917

1818283

54809

] (C7=

C8)+120575(C7minus

H)

1529037

1166

9056

1519870

1880

16642

120575(CH2C12

sciss

oring)

1500

104

20636

1317

81496912

43736

27878

120575(CH2C11

sciss

oring)

1482282

55577

3273

1489073

93803

1353

0](r

ingCminusC

andCminusN


twisting)

144819

045498

9248

1443952

60681

26451

120575 (O6minus

H)+120574(C

H2C12

overtone)

1427302

23576

7779

1427587

30543

20827

120575 (N2minus

H)+120574(C

H2C12

overtone)

1421510

3616

1511

1423682

23509

6940

120575 (N2minus

HC7minus

H)+120574(C

H2C11

overtone)

1390505

118205

7611

138718

1119

856

11122

120574(CminusHC11


H)

1380598

3819

640

217

1380309

114269

1316

49120575 (O6minus

HC7minus

H )+120574(C

H2C11

twisting)

1347554

8316

479

091349457

1297

4913904

120575 (O6minus

HC7minus

HN2minus


andC12)

1281458

4432

317485

1284076

103003

28210

120574(CH2C12


1256870

106831

7770

1240

649

71580

4513

9] (C8minus

FN2minus

C10 )+120575(C7minusH)+120574(C

H2C12

twisting)

1225483

75439

2778

1231243

282155

6081

120574(CH2C11

and

C12t


HC7minus

HN2minus

H)

11712

7571265

6885

1178572

74246

37119

](ringCminusN


HC7minus

HN2minus


andC12)

1152566

18908

10654

1144897

77474

17510


HC7minus

H)+120574 (CminusHC11 )

111400

040

616

3788

1092868

41455

9179


H)

1078303

39558

0562

1065832

1210

3817

64120575 (O6minus

H)+120588(C

H2C11

and

C12)

950975

14994

4003

9574

2426819

6760


HC7minus

H)

9019

4924808

3319

926124

3339

48721

120574(C7minus

H)

888823

16915

2971

888838

38112

6208

120575 (N2minus

HC7minus

H)+120588(

CH2C11

and

C12)+](C11minus

C12 )

856699

1215

76746

85646

428472

12028

120575 (N2minus

H)+120588(

CH2C11)+](C11minus

C12 )

7775

9711367

16247

782228

10639

48556

120575(rin

gCNC

NCN

bend

ing)

7518

940787

0694

752374

0591

2834


O5N2C8C9o

utof

planedeform

ation)

7412

8068559

0783

7377

5395416

1452

120574(N2minus

Hw

agging)+120574(r

ingO4N1N2C10

O5N2C8C9o

utof

planedeform

ation)

689145

1874

44013

6897

4533709

6088

120588(CH2C12)+](N1minus

C11 )+120575(rin

gN2C10N1b

ending)

673146

41930

1197

668088

2271

6203

120574(N2minus

Hw

agging)

6673

0512

192541

654352

93406

1226

120588(CH2C11)+120575(rin


ending)

563675

9497

2281

563724

1131

65625

120575(NCC

N1C11C12

bend

ing)+120588(C

H2C12)

5014

5814

9096

74503295

3892

19791

120575(CCOC11C12O6b

ending)+120575(

ringC8C7N1O4C10N2b

ending)

436878

83784

2489

435560

35623

7042

120574(O6minus

Hw

agging)+120575(

ringN2C10N1C11N1C7b

ending)

408328

1272

9013

8440

9922

9849

1315

120574(O6minus

Hw

agging)+120574(

ringC8C7N1C10

outo

fplanedeform

ation)

alim

itedto

thedescrip

tionof

stron

gvibrationalm

odes

ofthestu

died

moleculeandtherepo

rted

vibrationalm

odes

arethoseof

thestu

died

moleculein

gasp

hase

althou

ghmanydescrip

tions

areidenticalin

the

twomedia(in

gasa

ndwater)

b]] sand

] asstr

etching(sim

plesymmetric

and

asym

metric

)120575inplaneb

ending

(sim

plesciss

oring)120574out

ofplaneb

ending

(twistingovertonew

agging

deformation)120588

rocking


0 500 1000 1500 2000 2500 3000 3500 4000

0

500

1000

1500

2000

2500

IR In

tens

ity (K

mm

ol)


0 500 1000 1500 2000 2500 3000 3500 40000

50

100

150

200

250

300

350

400

450

500



Ram

an A

ctiv

ity (

4A

MU

)









HOMO (-7122 eV) LUMO (-1955 eV)











0 1 2 3 4 5

0

1

2

3

Energy (eV)


5167 eV







4 Conclusions


0m and S0m




Data Availability




Acknowledgments




References



























































Shock and Vibration





Volume 2018














Geophysics



Volume 2018




Volume 2018






Journal of

Chemistry




RotatingMachinery







(a) (b)


(c)









V (r) = sumA


120588 (r1015840)1003816100381610038161003816r1015840 minus r1003816100381610038161003816

dr1015840 (2)







0m


H0m = 000017T2 + 007498T + 36419947(R2 = 099951)

(3)


(4)


Table1Molecular

geom

etric

alparameterso

fthe

studied

moleculeingasp

haseaqu

eous

solutio

nandtheh

ollowspaceo

fthe

nano

tubesS

WCN

T(120)SW

CNT(140)andSW

CNT(160)

Gas

Phase

Aqueou

ssolutio

nInsid

ecapp

ed-SWCN

T(120)

Insid

ecapp

ed-SWCN

T(140)

Insid

ecapp

ed-SWCN

T(160)

Experim

ental

[4]

B3LY

P6minus

31+G

(d)

B3LY

P6minus

31+G

(d)

ONIO

M(B3LYP

6minus31

+G(d)U

FF)

ONIO

M(B3LYP

6minus31

+G(d)U

FF)

ONIO

M(B3LYP

6minus31

+G(d)U

FF)

Bond

lengths

(A)

N1-C

1013

9213

8813

8213

9313

911373(3)

N1-C

713

8213

7713

8113

8113

821376(3)

N1-C

1114

7114

7614

8114

7014

721479(3)

N2-C1

013

8413

8513

8013

8513

841374(3)

N2-C9

1407

1397

1405

1407

1408

1385(3)

F3-C

813

4513

5213

4313

4513

441355(3)

O4-C1

012

2812

3112

2812

2712

281228(3)

O5-C9

1219

1230

1218

1219

1219

1225(3)

O6-C1

214

1514

2614

1014

1614

151418(3)

C7-C

813

4913

5013

4813

4813

491329(4)

C8-C

914

5914

4914

5314

5914

591431(4)

C11-C

1215

3415

3015

4315

3415

331511(4)

Bond

angle

s(∘ )

C10-N1-C

71213

151213

28120132

1212

841212

661212(2)

C10-N1-C

11117662

11819

4118

819

118043

117666

1199(2)

C7-N

1-C11

120947

120473

120966

120457

120997

1189(2)

C10-N2-C9

128872

128384

130159

1290

67128910

1282(2)

C8-C

7-N1

122075

1216

79123498

122288

122084

1213(2)

C7-C

8-F3

120673

120775

120968

120711

120725

1206(2)

C7-C

8-C9

1217

701219

411212

671216

11121742

1225(2)

F3-C

8-C9

117557

117281

11776

5117667

11753

31169(2)

O5-C9

-N2

1218

741218

501218

631219

091218

651208(2)

O5-C9

-C8

126769

126316

1277

08126747

126814

1273(2)

N2-C9

-C8

111357

111833

110428

111341

111319

1119(2)

O4-C1

0-N2

122497

1219

7612240

4122560

122546

1216(2)

O4-C1

0-N1

122957

123204

123087

123128

122909

1234(2)

N2-C1

0-N1

114543

114820

114509

11431

1114

543

1149(2)

N1-C

11-C1

2113

368

11332

8115

139

113407

113723

1115(2)

O6-C1

2-C1

1113

637

113499

114512

113704

113940

1119(2)


0 100 200 300 400 500 600 700 800 900 1000350375400425450475500525550575600

Temperature (K)

（0 Ｇ

(KJm

ol)

(a)

0 100 200 300 400 500 600 700 800 900 1000

050

100150200250300350400

Temperature (K)

0 Ｇ

(KJm

ol)

minus50

minus100

minus150

minus200

(b)

0 100 200 300 400 500 600 700 800 900 1000250300350400450500550600650700750

Temperature (K)

３0 Ｇ

(KJm

ol)

(c)


(50minus950 K)

S0m = minus000021T2 + 073125T + 2273794(R2 = 099960)

(5)


0m and S0m of the





100 200 300 400 500 600 700 800 900Temperature (K)


minus40

minus38

minus36

minus34

minus32

minus30

minus28

minus42

Δ（

４(K

calm

ol)

(a)

100 200 300 400 500 600 700 800 900Temperature (K)


minus40

minus35

minus25

minus30

minus45

Δ３４

(cal

mol

K)

(b)

100 200 300 400 500 600 700 800 900

0

Temperature (K)


minus40

minus30

minus20

minus10

Δ

４(K

calm

ol)

(c)

100 200 300 400 500 600 700 800 9000

005

01

015

02

Temperature (K)

LogK


(d)









ency

(cmminus1)IR

intensity

(Kmm

ol)Ra

man

activ

ity(A4A

MU)andassig

nmentsof

thestu

died

moleculeat

B3LY

P6-31+G

(d)levelin

gasp

hase

andaqueou

ssolutio

nGas

phase

Aqueou

ssolution

ASSIG

NMEN

TSab

Frequency

IRintensity

Raman

activ

ityFrequency

IRIntensity

Raman

activ

ity3693369

69061

44508

3705977

87657

9819

2](06minus

H)

3586430

75248

74241

3577938

115905

1495

67](N2minus

H)

3238231

2895

77440

3251219

6661

182559

](C7minus

H)

3141099

6603

4217

33160

495

8380

10664

1] a

s(CH2C11

andC12)

3084940

3319

7113

127

3111124

43204

166701

] s(C

H2C11)+]

as(C

H2C12)

308112

423687

97655

3104

464

21819

312681

] s(C

H2C11)+]

as(C

H2C12)

3000

562

7415

1202427

3031451

86618

368806

] s(C

H2C12)

178916

9538145

9916

21740

087

4217

501273

85] (C=0C9a


H)

1762630

7173

545220

1707784

1468833

235994

] (C10=O)+120575(N2minus

H)

1711453

1010

795119

7169917

1818283

54809

] (C7=

C8)+120575(C7minus

H)

1529037

1166

9056

1519870

1880

16642

120575(CH2C12

sciss

oring)

1500

104

20636

1317

81496912

43736

27878

120575(CH2C11

sciss

oring)

1482282

55577

3273

1489073

93803

1353

0](r

ingCminusC

andCminusN


twisting)

144819

045498

9248

1443952

60681

26451

120575 (O6minus

H)+120574(C

H2C12

overtone)

1427302

23576

7779

1427587

30543

20827

120575 (N2minus

H)+120574(C

H2C12

overtone)

1421510

3616

1511

1423682

23509

6940

120575 (N2minus

HC7minus

H)+120574(C

H2C11

overtone)

1390505

118205

7611

138718

1119

856

11122

120574(CminusHC11


H)

1380598

3819

640

217

1380309

114269

1316

49120575 (O6minus

HC7minus

H )+120574(C

H2C11

twisting)

1347554

8316

479

091349457

1297

4913904

120575 (O6minus

HC7minus

HN2minus


andC12)

1281458

4432

317485

1284076

103003

28210

120574(CH2C12


1256870

106831

7770

1240

649

71580

4513

9] (C8minus

FN2minus

C10 )+120575(C7minusH)+120574(C

H2C12

twisting)

1225483

75439

2778

1231243

282155

6081

120574(CH2C11

and

C12t


HC7minus

HN2minus

H)

11712

7571265

6885

1178572

74246

37119

](ringCminusN


HC7minus

HN2minus


andC12)

1152566

18908

10654

1144897

77474

17510


HC7minus

H)+120574 (CminusHC11 )

111400

040

616

3788

1092868

41455

9179


H)

1078303

39558

0562

1065832

1210

3817

64120575 (O6minus

H)+120588(C

H2C11

and

C12)

950975

14994

4003

9574

2426819

6760


HC7minus

H)

9019

4924808

3319

926124

3339

48721

120574(C7minus

H)

888823

16915

2971

888838

38112

6208

120575 (N2minus

HC7minus

H)+120588(

CH2C11

and

C12)+](C11minus

C12 )

856699

1215

76746

85646

428472

12028

120575 (N2minus

H)+120588(

CH2C11)+](C11minus

C12 )

7775

9711367

16247

782228

10639

48556

120575(rin

gCNC

NCN

bend

ing)

7518

940787

0694

752374

0591

2834


O5N2C8C9o

utof

planedeform

ation)

7412

8068559

0783

7377

5395416

1452

120574(N2minus

Hw

agging)+120574(r

ingO4N1N2C10

O5N2C8C9o

utof

planedeform

ation)

689145

1874

44013

6897

4533709

6088

120588(CH2C12)+](N1minus

C11 )+120575(rin

gN2C10N1b

ending)

673146

41930

1197

668088

2271

6203

120574(N2minus

Hw

agging)

6673

0512

192541

654352

93406

1226

120588(CH2C11)+120575(rin


ending)

563675

9497

2281

563724

1131

65625

120575(NCC

N1C11C12

bend

ing)+120588(C

H2C12)

5014

5814

9096

74503295

3892

19791

120575(CCOC11C12O6b

ending)+120575(

ringC8C7N1O4C10N2b

ending)

436878

83784

2489

435560

35623

7042

120574(O6minus

Hw

agging)+120575(

ringN2C10N1C11N1C7b

ending)

408328

1272

9013

8440

9922

9849

1315

120574(O6minus

Hw

agging)+120574(

ringC8C7N1C10

outo

fplanedeform

ation)

alim

itedto

thedescrip

tionof

stron

gvibrationalm

odes

ofthestu

died

moleculeandtherepo

rted

vibrationalm

odes

arethoseof

thestu

died

moleculein

gasp

hase

althou

ghmanydescrip

tions

areidenticalin

the

twomedia(in

gasa

ndwater)

b]] sand

] asstr

etching(sim

plesymmetric

and

asym

metric

)120575inplaneb

ending

(sim

plesciss

oring)120574out

ofplaneb

ending

(twistingovertonew

agging

deformation)120588

rocking


0 500 1000 1500 2000 2500 3000 3500 4000

0

500

1000

1500

2000

2500

IR In

tens

ity (K

mm

ol)


0 500 1000 1500 2000 2500 3000 3500 40000

50

100

150

200

250

300

350

400

450

500



Ram

an A

ctiv

ity (

4A

MU

)









HOMO (-7122 eV) LUMO (-1955 eV)











0 1 2 3 4 5

0

1

2

3

Energy (eV)


5167 eV







4 Conclusions


0m and S0m




Data Availability




Acknowledgments




References



























































Shock and Vibration





Volume 2018














Geophysics



Volume 2018




Volume 2018






Journal of

Chemistry




RotatingMachinery








V (r) = sumA


120588 (r1015840)1003816100381610038161003816r1015840 minus r1003816100381610038161003816

dr1015840 (2)







0m


H0m = 000017T2 + 007498T + 36419947(R2 = 099951)

(3)


(4)


Table1Molecular

geom

etric

alparameterso

fthe

studied

moleculeingasp

haseaqu

eous

solutio

nandtheh

ollowspaceo

fthe

nano

tubesS

WCN

T(120)SW

CNT(140)andSW

CNT(160)

Gas

Phase

Aqueou

ssolutio

nInsid

ecapp

ed-SWCN

T(120)

Insid

ecapp

ed-SWCN

T(140)

Insid

ecapp

ed-SWCN

T(160)

Experim

ental

[4]

B3LY

P6minus

31+G

(d)

B3LY

P6minus

31+G

(d)

ONIO

M(B3LYP

6minus31

+G(d)U

FF)

ONIO

M(B3LYP

6minus31

+G(d)U

FF)

ONIO

M(B3LYP

6minus31

+G(d)U

FF)

Bond

lengths

(A)

N1-C

1013

9213

8813

8213

9313

911373(3)

N1-C

713

8213

7713

8113

8113

821376(3)

N1-C

1114

7114

7614

8114

7014

721479(3)

N2-C1

013

8413

8513

8013

8513

841374(3)

N2-C9

1407

1397

1405

1407

1408

1385(3)

F3-C

813

4513

5213

4313

4513

441355(3)

O4-C1

012

2812

3112

2812

2712

281228(3)

O5-C9

1219

1230

1218

1219

1219

1225(3)

O6-C1

214

1514

2614

1014

1614

151418(3)

C7-C

813

4913

5013

4813

4813

491329(4)

C8-C

914

5914

4914

5314

5914

591431(4)

C11-C

1215

3415

3015

4315

3415

331511(4)

Bond

angle

s(∘ )

C10-N1-C

71213

151213

28120132

1212

841212

661212(2)

C10-N1-C

11117662

11819

4118

819

118043

117666

1199(2)

C7-N

1-C11

120947

120473

120966

120457

120997

1189(2)

C10-N2-C9

128872

128384

130159

1290

67128910

1282(2)

C8-C

7-N1

122075

1216

79123498

122288

122084

1213(2)

C7-C

8-F3

120673

120775

120968

120711

120725

1206(2)

C7-C

8-C9

1217

701219

411212

671216

11121742

1225(2)

F3-C

8-C9

117557

117281

11776

5117667

11753

31169(2)

O5-C9

-N2

1218

741218

501218

631219

091218

651208(2)

O5-C9

-C8

126769

126316

1277

08126747

126814

1273(2)

N2-C9

-C8

111357

111833

110428

111341

111319

1119(2)

O4-C1

0-N2

122497

1219

7612240

4122560

122546

1216(2)

O4-C1

0-N1

122957

123204

123087

123128

122909

1234(2)

N2-C1

0-N1

114543

114820

114509

11431

1114

543

1149(2)

N1-C

11-C1

2113

368

11332

8115

139

113407

113723

1115(2)

O6-C1

2-C1

1113

637

113499

114512

113704

113940

1119(2)


0 100 200 300 400 500 600 700 800 900 1000350375400425450475500525550575600

Temperature (K)

（0 Ｇ

(KJm

ol)

(a)

0 100 200 300 400 500 600 700 800 900 1000

050

100150200250300350400

Temperature (K)

0 Ｇ

(KJm

ol)

minus50

minus100

minus150

minus200

(b)

0 100 200 300 400 500 600 700 800 900 1000250300350400450500550600650700750

Temperature (K)

３0 Ｇ

(KJm

ol)

(c)


(50minus950 K)

S0m = minus000021T2 + 073125T + 2273794(R2 = 099960)

(5)


0m and S0m of the





100 200 300 400 500 600 700 800 900Temperature (K)


minus40

minus38

minus36

minus34

minus32

minus30

minus28

minus42

Δ（

４(K

calm

ol)

(a)

100 200 300 400 500 600 700 800 900Temperature (K)


minus40

minus35

minus25

minus30

minus45

Δ３４

(cal

mol

K)

(b)

100 200 300 400 500 600 700 800 900

0

Temperature (K)


minus40

minus30

minus20

minus10

Δ

４(K

calm

ol)

(c)

100 200 300 400 500 600 700 800 9000

005

01

015

02

Temperature (K)

LogK


(d)









ency

(cmminus1)IR

intensity

(Kmm

ol)Ra

man

activ

ity(A4A

MU)andassig

nmentsof

thestu

died

moleculeat

B3LY

P6-31+G

(d)levelin

gasp

hase

andaqueou

ssolutio

nGas

phase

Aqueou

ssolution

ASSIG

NMEN

TSab

Frequency

IRintensity

Raman

activ

ityFrequency

IRIntensity

Raman

activ

ity3693369

69061

44508

3705977

87657

9819

2](06minus

H)

3586430

75248

74241

3577938

115905

1495

67](N2minus

H)

3238231

2895

77440

3251219

6661

182559

](C7minus

H)

3141099

6603

4217

33160

495

8380

10664

1] a

s(CH2C11

andC12)

3084940

3319

7113

127

3111124

43204

166701

] s(C

H2C11)+]

as(C

H2C12)

308112

423687

97655

3104

464

21819

312681

] s(C

H2C11)+]

as(C

H2C12)

3000

562

7415

1202427

3031451

86618

368806

] s(C

H2C12)

178916

9538145

9916

21740

087

4217

501273

85] (C=0C9a


H)

1762630

7173

545220

1707784

1468833

235994

] (C10=O)+120575(N2minus

H)

1711453

1010

795119

7169917

1818283

54809

] (C7=

C8)+120575(C7minus

H)

1529037

1166

9056

1519870

1880

16642

120575(CH2C12

sciss

oring)

1500

104

20636

1317

81496912

43736

27878

120575(CH2C11

sciss

oring)

1482282

55577

3273

1489073

93803

1353

0](r

ingCminusC

andCminusN


twisting)

144819

045498

9248

1443952

60681

26451

120575 (O6minus

H)+120574(C

H2C12

overtone)

1427302

23576

7779

1427587

30543

20827

120575 (N2minus

H)+120574(C

H2C12

overtone)

1421510

3616

1511

1423682

23509

6940

120575 (N2minus

HC7minus

H)+120574(C

H2C11

overtone)

1390505

118205

7611

138718

1119

856

11122

120574(CminusHC11


H)

1380598

3819

640

217

1380309

114269

1316

49120575 (O6minus

HC7minus

H )+120574(C

H2C11

twisting)

1347554

8316

479

091349457

1297

4913904

120575 (O6minus

HC7minus

HN2minus


andC12)

1281458

4432

317485

1284076

103003

28210

120574(CH2C12


1256870

106831

7770

1240

649

71580

4513

9] (C8minus

FN2minus

C10 )+120575(C7minusH)+120574(C

H2C12

twisting)

1225483

75439

2778

1231243

282155

6081

120574(CH2C11

and

C12t


HC7minus

HN2minus

H)

11712

7571265

6885

1178572

74246

37119

](ringCminusN


HC7minus

HN2minus


andC12)

1152566

18908

10654

1144897

77474

17510


HC7minus

H)+120574 (CminusHC11 )

111400

040

616

3788

1092868

41455

9179


H)

1078303

39558

0562

1065832

1210

3817

64120575 (O6minus

H)+120588(C

H2C11

and

C12)

950975

14994

4003

9574

2426819

6760


HC7minus

H)

9019

4924808

3319

926124

3339

48721

120574(C7minus

H)

888823

16915

2971

888838

38112

6208

120575 (N2minus

HC7minus

H)+120588(

CH2C11

and

C12)+](C11minus

C12 )

856699

1215

76746

85646

428472

12028

120575 (N2minus

H)+120588(

CH2C11)+](C11minus

C12 )

7775

9711367

16247

782228

10639

48556

120575(rin

gCNC

NCN

bend

ing)

7518

940787

0694

752374

0591

2834


O5N2C8C9o

utof

planedeform

ation)

7412

8068559

0783

7377

5395416

1452

120574(N2minus

Hw

agging)+120574(r

ingO4N1N2C10

O5N2C8C9o

utof

planedeform

ation)

689145

1874

44013

6897

4533709

6088

120588(CH2C12)+](N1minus

C11 )+120575(rin

gN2C10N1b

ending)

673146

41930

1197

668088

2271

6203

120574(N2minus

Hw

agging)

6673

0512

192541

654352

93406

1226

120588(CH2C11)+120575(rin


ending)

563675

9497

2281

563724

1131

65625

120575(NCC

N1C11C12

bend

ing)+120588(C

H2C12)

5014

5814

9096

74503295

3892

19791

120575(CCOC11C12O6b

ending)+120575(

ringC8C7N1O4C10N2b

ending)

436878

83784

2489

435560

35623

7042

120574(O6minus

Hw

agging)+120575(

ringN2C10N1C11N1C7b

ending)

408328

1272

9013

8440

9922

9849

1315

120574(O6minus

Hw

agging)+120574(

ringC8C7N1C10

outo

fplanedeform

ation)

alim

itedto

thedescrip

tionof

stron

gvibrationalm

odes

ofthestu

died

moleculeandtherepo

rted

vibrationalm

odes

arethoseof

thestu

died

moleculein

gasp

hase

althou

ghmanydescrip

tions

areidenticalin

the

twomedia(in

gasa

ndwater)

b]] sand

] asstr

etching(sim

plesymmetric

and

asym

metric

)120575inplaneb

ending

(sim

plesciss

oring)120574out

ofplaneb

ending

(twistingovertonew

agging

deformation)120588

rocking


0 500 1000 1500 2000 2500 3000 3500 4000

0

500

1000

1500

2000

2500

IR In

tens

ity (K

mm

ol)


0 500 1000 1500 2000 2500 3000 3500 40000

50

100

150

200

250

300

350

400

450

500



Ram

an A

ctiv

ity (

4A

MU

)









HOMO (-7122 eV) LUMO (-1955 eV)











0 1 2 3 4 5

0

1

2

3

Energy (eV)


5167 eV







4 Conclusions


0m and S0m




Data Availability




Acknowledgments




References



























































Shock and Vibration





Volume 2018














Geophysics



Volume 2018




Volume 2018






Journal of

Chemistry




RotatingMachinery






Table1Molecular

geom

etric

alparameterso

fthe

studied

moleculeingasp

haseaqu

eous

solutio

nandtheh

ollowspaceo

fthe

nano

tubesS

WCN

T(120)SW

CNT(140)andSW

CNT(160)

Gas

Phase

Aqueou

ssolutio

nInsid

ecapp

ed-SWCN

T(120)

Insid

ecapp

ed-SWCN

T(140)

Insid

ecapp

ed-SWCN

T(160)

Experim

ental

[4]

B3LY

P6minus

31+G

(d)

B3LY

P6minus

31+G

(d)

ONIO

M(B3LYP

6minus31

+G(d)U

FF)

ONIO

M(B3LYP

6minus31

+G(d)U

FF)

ONIO

M(B3LYP

6minus31

+G(d)U

FF)

Bond

lengths

(A)

N1-C

1013

9213

8813

8213

9313

911373(3)

N1-C

713

8213

7713

8113

8113

821376(3)

N1-C

1114

7114

7614

8114

7014

721479(3)

N2-C1

013

8413

8513

8013

8513

841374(3)

N2-C9

1407

1397

1405

1407

1408

1385(3)

F3-C

813

4513

5213

4313

4513

441355(3)

O4-C1

012

2812

3112

2812

2712

281228(3)

O5-C9

1219

1230

1218

1219

1219

1225(3)

O6-C1

214

1514

2614

1014

1614

151418(3)

C7-C

813

4913

5013

4813

4813

491329(4)

C8-C

914

5914

4914

5314

5914

591431(4)

C11-C

1215

3415

3015

4315

3415

331511(4)

Bond

angle

s(∘ )

C10-N1-C

71213

151213

28120132

1212

841212

661212(2)

C10-N1-C

11117662

11819

4118

819

118043

117666

1199(2)

C7-N

1-C11

120947

120473

120966

120457

120997

1189(2)

C10-N2-C9

128872

128384

130159

1290

67128910

1282(2)

C8-C

7-N1

122075

1216

79123498

122288

122084

1213(2)

C7-C

8-F3

120673

120775

120968

120711

120725

1206(2)

C7-C

8-C9

1217

701219

411212

671216

11121742

1225(2)

F3-C

8-C9

117557

117281

11776

5117667

11753

31169(2)

O5-C9

-N2

1218

741218

501218

631219

091218

651208(2)

O5-C9

-C8

126769

126316

1277

08126747

126814

1273(2)

N2-C9

-C8

111357

111833

110428

111341

111319

1119(2)

O4-C1

0-N2

122497

1219

7612240

4122560

122546

1216(2)

O4-C1

0-N1

122957

123204

123087

123128

122909

1234(2)

N2-C1

0-N1

114543

114820

114509

11431

1114

543

1149(2)

N1-C

11-C1

2113

368

11332

8115

139

113407

113723

1115(2)

O6-C1

2-C1

1113

637

113499

114512

113704

113940

1119(2)


0 100 200 300 400 500 600 700 800 900 1000350375400425450475500525550575600

Temperature (K)

（0 Ｇ

(KJm

ol)

(a)

0 100 200 300 400 500 600 700 800 900 1000

050

100150200250300350400

Temperature (K)

0 Ｇ

(KJm

ol)

minus50

minus100

minus150

minus200

(b)

0 100 200 300 400 500 600 700 800 900 1000250300350400450500550600650700750

Temperature (K)

３0 Ｇ

(KJm

ol)

(c)


(50minus950 K)

S0m = minus000021T2 + 073125T + 2273794(R2 = 099960)

(5)


0m and S0m of the





100 200 300 400 500 600 700 800 900Temperature (K)


minus40

minus38

minus36

minus34

minus32

minus30

minus28

minus42

Δ（

４(K

calm

ol)

(a)

100 200 300 400 500 600 700 800 900Temperature (K)


minus40

minus35

minus25

minus30

minus45

Δ３４

(cal

mol

K)

(b)

100 200 300 400 500 600 700 800 900

0

Temperature (K)


minus40

minus30

minus20

minus10

Δ

４(K

calm

ol)

(c)

100 200 300 400 500 600 700 800 9000

005

01

015

02

Temperature (K)

LogK


(d)









ency

(cmminus1)IR

intensity

(Kmm

ol)Ra

man

activ

ity(A4A

MU)andassig

nmentsof

thestu

died

moleculeat

B3LY

P6-31+G

(d)levelin

gasp

hase

andaqueou

ssolutio

nGas

phase

Aqueou

ssolution

ASSIG

NMEN

TSab

Frequency

IRintensity

Raman

activ

ityFrequency

IRIntensity

Raman

activ

ity3693369

69061

44508

3705977

87657

9819

2](06minus

H)

3586430

75248

74241

3577938

115905

1495

67](N2minus

H)

3238231

2895

77440

3251219

6661

182559

](C7minus

H)

3141099

6603

4217

33160

495

8380

10664

1] a

s(CH2C11

andC12)

3084940

3319

7113

127

3111124

43204

166701

] s(C

H2C11)+]

as(C

H2C12)

308112

423687

97655

3104

464

21819

312681

] s(C

H2C11)+]

as(C

H2C12)

3000

562

7415

1202427

3031451

86618

368806

] s(C

H2C12)

178916

9538145

9916

21740

087

4217

501273

85] (C=0C9a


H)

1762630

7173

545220

1707784

1468833

235994

] (C10=O)+120575(N2minus

H)

1711453

1010

795119

7169917

1818283

54809

] (C7=

C8)+120575(C7minus

H)

1529037

1166

9056

1519870

1880

16642

120575(CH2C12

sciss

oring)

1500

104

20636

1317

81496912

43736

27878

120575(CH2C11

sciss

oring)

1482282

55577

3273

1489073

93803

1353

0](r

ingCminusC

andCminusN


twisting)

144819

045498

9248

1443952

60681

26451

120575 (O6minus

H)+120574(C

H2C12

overtone)

1427302

23576

7779

1427587

30543

20827

120575 (N2minus

H)+120574(C

H2C12

overtone)

1421510

3616

1511

1423682

23509

6940

120575 (N2minus

HC7minus

H)+120574(C

H2C11

overtone)

1390505

118205

7611

138718

1119

856

11122

120574(CminusHC11


H)

1380598

3819

640

217

1380309

114269

1316

49120575 (O6minus

HC7minus

H )+120574(C

H2C11

twisting)

1347554

8316

479

091349457

1297

4913904

120575 (O6minus

HC7minus

HN2minus


andC12)

1281458

4432

317485

1284076

103003

28210

120574(CH2C12


1256870

106831

7770

1240

649

71580

4513

9] (C8minus

FN2minus

C10 )+120575(C7minusH)+120574(C

H2C12

twisting)

1225483

75439

2778

1231243

282155

6081

120574(CH2C11

and

C12t


HC7minus

HN2minus

H)

11712

7571265

6885

1178572

74246

37119

](ringCminusN


HC7minus

HN2minus


andC12)

1152566

18908

10654

1144897

77474

17510


HC7minus

H)+120574 (CminusHC11 )

111400

040

616

3788

1092868

41455

9179


H)

1078303

39558

0562

1065832

1210

3817

64120575 (O6minus

H)+120588(C

H2C11

and

C12)

950975

14994

4003

9574

2426819

6760


HC7minus

H)

9019

4924808

3319

926124

3339

48721

120574(C7minus

H)

888823

16915

2971

888838

38112

6208

120575 (N2minus

HC7minus

H)+120588(

CH2C11

and

C12)+](C11minus

C12 )

856699

1215

76746

85646

428472

12028

120575 (N2minus

H)+120588(

CH2C11)+](C11minus

C12 )

7775

9711367

16247

782228

10639

48556

120575(rin

gCNC

NCN

bend

ing)

7518

940787

0694

752374

0591

2834


O5N2C8C9o

utof

planedeform

ation)

7412

8068559

0783

7377

5395416

1452

120574(N2minus

Hw

agging)+120574(r

ingO4N1N2C10

O5N2C8C9o

utof

planedeform

ation)

689145

1874

44013

6897

4533709

6088

120588(CH2C12)+](N1minus

C11 )+120575(rin

gN2C10N1b

ending)

673146

41930

1197

668088

2271

6203

120574(N2minus

Hw

agging)

6673

0512

192541

654352

93406

1226

120588(CH2C11)+120575(rin


ending)

563675

9497

2281

563724

1131

65625

120575(NCC

N1C11C12

bend

ing)+120588(C

H2C12)

5014

5814

9096

74503295

3892

19791

120575(CCOC11C12O6b

ending)+120575(

ringC8C7N1O4C10N2b

ending)

436878

83784

2489

435560

35623

7042

120574(O6minus

Hw

agging)+120575(

ringN2C10N1C11N1C7b

ending)

408328

1272

9013

8440

9922

9849

1315

120574(O6minus

Hw

agging)+120574(

ringC8C7N1C10

outo

fplanedeform

ation)

alim

itedto

thedescrip

tionof

stron

gvibrationalm

odes

ofthestu

died

moleculeandtherepo

rted

vibrationalm

odes

arethoseof

thestu

died

moleculein

gasp

hase

althou

ghmanydescrip

tions

areidenticalin

the

twomedia(in

gasa

ndwater)

b]] sand

] asstr

etching(sim

plesymmetric

and

asym

metric

)120575inplaneb

ending

(sim

plesciss

oring)120574out

ofplaneb

ending

(twistingovertonew

agging

deformation)120588

rocking


0 500 1000 1500 2000 2500 3000 3500 4000

0

500

1000

1500

2000

2500

IR In

tens

ity (K

mm

ol)


0 500 1000 1500 2000 2500 3000 3500 40000

50

100

150

200

250

300

350

400

450

500



Ram

an A

ctiv

ity (

4A

MU

)









HOMO (-7122 eV) LUMO (-1955 eV)











0 1 2 3 4 5

0

1

2

3

Energy (eV)


5167 eV







4 Conclusions


0m and S0m




Data Availability




Acknowledgments




References



























































Shock and Vibration





Volume 2018














Geophysics



Volume 2018




Volume 2018






Journal of

Chemistry




RotatingMachinery






0 100 200 300 400 500 600 700 800 900 1000350375400425450475500525550575600

Temperature (K)

（0 Ｇ

(KJm

ol)

(a)

0 100 200 300 400 500 600 700 800 900 1000

050

100150200250300350400

Temperature (K)

0 Ｇ

(KJm

ol)

minus50

minus100

minus150

minus200

(b)

0 100 200 300 400 500 600 700 800 900 1000250300350400450500550600650700750

Temperature (K)

３0 Ｇ

(KJm

ol)

(c)


(50minus950 K)

S0m = minus000021T2 + 073125T + 2273794(R2 = 099960)

(5)


0m and S0m of the





100 200 300 400 500 600 700 800 900Temperature (K)


minus40

minus38

minus36

minus34

minus32

minus30

minus28

minus42

Δ（

４(K

calm

ol)

(a)

100 200 300 400 500 600 700 800 900Temperature (K)


minus40

minus35

minus25

minus30

minus45

Δ３４

(cal

mol

K)

(b)

100 200 300 400 500 600 700 800 900

0

Temperature (K)


minus40

minus30

minus20

minus10

Δ

４(K

calm

ol)

(c)

100 200 300 400 500 600 700 800 9000

005

01

015

02

Temperature (K)

LogK


(d)









ency

(cmminus1)IR

intensity

(Kmm

ol)Ra

man

activ

ity(A4A

MU)andassig

nmentsof

thestu

died

moleculeat

B3LY

P6-31+G

(d)levelin

gasp

hase

andaqueou

ssolutio

nGas

phase

Aqueou

ssolution

ASSIG

NMEN

TSab

Frequency

IRintensity

Raman

activ

ityFrequency

IRIntensity

Raman

activ

ity3693369

69061

44508

3705977

87657

9819

2](06minus

H)

3586430

75248

74241

3577938

115905

1495

67](N2minus

H)

3238231

2895

77440

3251219

6661

182559

](C7minus

H)

3141099

6603

4217

33160

495

8380

10664

1] a

s(CH2C11

andC12)

3084940

3319

7113

127

3111124

43204

166701

] s(C

H2C11)+]

as(C

H2C12)

308112

423687

97655

3104

464

21819

312681

] s(C

H2C11)+]

as(C

H2C12)

3000

562

7415

1202427

3031451

86618

368806

] s(C

H2C12)

178916

9538145

9916

21740

087

4217

501273

85] (C=0C9a


H)

1762630

7173

545220

1707784

1468833

235994

] (C10=O)+120575(N2minus

H)

1711453

1010

795119

7169917

1818283

54809

] (C7=

C8)+120575(C7minus

H)

1529037

1166

9056

1519870

1880

16642

120575(CH2C12

sciss

oring)

1500

104

20636

1317

81496912

43736

27878

120575(CH2C11

sciss

oring)

1482282

55577

3273

1489073

93803

1353

0](r

ingCminusC

andCminusN


twisting)

144819

045498

9248

1443952

60681

26451

120575 (O6minus

H)+120574(C

H2C12

overtone)

1427302

23576

7779

1427587

30543

20827

120575 (N2minus

H)+120574(C

H2C12

overtone)

1421510

3616

1511

1423682

23509

6940

120575 (N2minus

HC7minus

H)+120574(C

H2C11

overtone)

1390505

118205

7611

138718

1119

856

11122

120574(CminusHC11


H)

1380598

3819

640

217

1380309

114269

1316

49120575 (O6minus

HC7minus

H )+120574(C

H2C11

twisting)

1347554

8316

479

091349457

1297

4913904

120575 (O6minus

HC7minus

HN2minus


andC12)

1281458

4432

317485

1284076

103003

28210

120574(CH2C12


1256870

106831

7770

1240

649

71580

4513

9] (C8minus

FN2minus

C10 )+120575(C7minusH)+120574(C

H2C12

twisting)

1225483

75439

2778

1231243

282155

6081

120574(CH2C11

and

C12t


HC7minus

HN2minus

H)

11712

7571265

6885

1178572

74246

37119

](ringCminusN


HC7minus

HN2minus


andC12)

1152566

18908

10654

1144897

77474

17510


HC7minus

H)+120574 (CminusHC11 )

111400

040

616

3788

1092868

41455

9179


H)

1078303

39558

0562

1065832

1210

3817

64120575 (O6minus

H)+120588(C

H2C11

and

C12)

950975

14994

4003

9574

2426819

6760


HC7minus

H)

9019

4924808

3319

926124

3339

48721

120574(C7minus

H)

888823

16915

2971

888838

38112

6208

120575 (N2minus

HC7minus

H)+120588(

CH2C11

and

C12)+](C11minus

C12 )

856699

1215

76746

85646

428472

12028

120575 (N2minus

H)+120588(

CH2C11)+](C11minus

C12 )

7775

9711367

16247

782228

10639

48556

120575(rin

gCNC

NCN

bend

ing)

7518

940787

0694

752374

0591

2834


O5N2C8C9o

utof

planedeform

ation)

7412

8068559

0783

7377

5395416

1452

120574(N2minus

Hw

agging)+120574(r

ingO4N1N2C10

O5N2C8C9o

utof

planedeform

ation)

689145

1874

44013

6897

4533709

6088

120588(CH2C12)+](N1minus

C11 )+120575(rin

gN2C10N1b

ending)

673146

41930

1197

668088

2271

6203

120574(N2minus

Hw

agging)

6673

0512

192541

654352

93406

1226

120588(CH2C11)+120575(rin


ending)

563675

9497

2281

563724

1131

65625

120575(NCC

N1C11C12

bend

ing)+120588(C

H2C12)

5014

5814

9096

74503295

3892

19791

120575(CCOC11C12O6b

ending)+120575(

ringC8C7N1O4C10N2b

ending)

436878

83784

2489

435560

35623

7042

120574(O6minus

Hw

agging)+120575(

ringN2C10N1C11N1C7b

ending)

408328

1272

9013

8440

9922

9849

1315

120574(O6minus

Hw

agging)+120574(

ringC8C7N1C10

outo

fplanedeform

ation)

alim

itedto

thedescrip

tionof

stron

gvibrationalm

odes

ofthestu

died

moleculeandtherepo

rted

vibrationalm

odes

arethoseof

thestu

died

moleculein

gasp

hase

althou

ghmanydescrip

tions

areidenticalin

the

twomedia(in

gasa

ndwater)

b]] sand

] asstr

etching(sim

plesymmetric

and

asym

metric

)120575inplaneb

ending

(sim

plesciss

oring)120574out

ofplaneb

ending

(twistingovertonew

agging

deformation)120588

rocking


0 500 1000 1500 2000 2500 3000 3500 4000

0

500

1000

1500

2000

2500

IR In

tens

ity (K

mm

ol)


0 500 1000 1500 2000 2500 3000 3500 40000

50

100

150

200

250

300

350

400

450

500



Ram

an A

ctiv

ity (

4A

MU

)









HOMO (-7122 eV) LUMO (-1955 eV)











0 1 2 3 4 5

0

1

2

3

Energy (eV)


5167 eV







4 Conclusions


0m and S0m




Data Availability




Acknowledgments




References



























































Shock and Vibration





Volume 2018














Geophysics



Volume 2018




Volume 2018






Journal of

Chemistry




RotatingMachinery






100 200 300 400 500 600 700 800 900Temperature (K)


minus40

minus38

minus36

minus34

minus32

minus30

minus28

minus42

Δ（

４(K

calm

ol)

(a)

100 200 300 400 500 600 700 800 900Temperature (K)


minus40

minus35

minus25

minus30

minus45

Δ３４

(cal

mol

K)

(b)

100 200 300 400 500 600 700 800 900

0

Temperature (K)


minus40

minus30

minus20

minus10

Δ

４(K

calm

ol)

(c)

100 200 300 400 500 600 700 800 9000

005

01

015

02

Temperature (K)

LogK


(d)









ency

(cmminus1)IR

intensity

(Kmm

ol)Ra

man

activ

ity(A4A

MU)andassig

nmentsof

thestu

died

moleculeat

B3LY

P6-31+G

(d)levelin

gasp

hase

andaqueou

ssolutio

nGas

phase

Aqueou

ssolution

ASSIG

NMEN

TSab

Frequency

IRintensity

Raman

activ

ityFrequency

IRIntensity

Raman

activ

ity3693369

69061

44508

3705977

87657

9819

2](06minus

H)

3586430

75248

74241

3577938

115905

1495

67](N2minus

H)

3238231

2895

77440

3251219

6661

182559

](C7minus

H)

3141099

6603

4217

33160

495

8380

10664

1] a

s(CH2C11

andC12)

3084940

3319

7113

127

3111124

43204

166701

] s(C

H2C11)+]

as(C

H2C12)

308112

423687

97655

3104

464

21819

312681

] s(C

H2C11)+]

as(C

H2C12)

3000

562

7415

1202427

3031451

86618

368806

] s(C

H2C12)

178916

9538145

9916

21740

087

4217

501273

85] (C=0C9a


H)

1762630

7173

545220

1707784

1468833

235994

] (C10=O)+120575(N2minus

H)

1711453

1010

795119

7169917

1818283

54809

] (C7=

C8)+120575(C7minus

H)

1529037

1166

9056

1519870

1880

16642

120575(CH2C12

sciss

oring)

1500

104

20636

1317

81496912

43736

27878

120575(CH2C11

sciss

oring)

1482282

55577

3273

1489073

93803

1353

0](r

ingCminusC

andCminusN


twisting)

144819

045498

9248

1443952

60681

26451

120575 (O6minus

H)+120574(C

H2C12

overtone)

1427302

23576

7779

1427587

30543

20827

120575 (N2minus

H)+120574(C

H2C12

overtone)

1421510

3616

1511

1423682

23509

6940

120575 (N2minus

HC7minus

H)+120574(C

H2C11

overtone)

1390505

118205

7611

138718

1119

856

11122

120574(CminusHC11


H)

1380598

3819

640

217

1380309

114269

1316

49120575 (O6minus

HC7minus

H )+120574(C

H2C11

twisting)

1347554

8316

479

091349457

1297

4913904

120575 (O6minus

HC7minus

HN2minus


andC12)

1281458

4432

317485

1284076

103003

28210

120574(CH2C12


1256870

106831

7770

1240

649

71580

4513

9] (C8minus

FN2minus

C10 )+120575(C7minusH)+120574(C

H2C12

twisting)

1225483

75439

2778

1231243

282155

6081

120574(CH2C11

and

C12t


HC7minus

HN2minus

H)

11712

7571265

6885

1178572

74246

37119

](ringCminusN


HC7minus

HN2minus


andC12)

1152566

18908

10654

1144897

77474

17510


HC7minus

H)+120574 (CminusHC11 )

111400

040

616

3788

1092868

41455

9179


H)

1078303

39558

0562

1065832

1210

3817

64120575 (O6minus

H)+120588(C

H2C11

and

C12)

950975

14994

4003

9574

2426819

6760


HC7minus

H)

9019

4924808

3319

926124

3339

48721

120574(C7minus

H)

888823

16915

2971

888838

38112

6208

120575 (N2minus

HC7minus

H)+120588(

CH2C11

and

C12)+](C11minus

C12 )

856699

1215

76746

85646

428472

12028

120575 (N2minus

H)+120588(

CH2C11)+](C11minus

C12 )

7775

9711367

16247

782228

10639

48556

120575(rin

gCNC

NCN

bend

ing)

7518

940787

0694

752374

0591

2834


O5N2C8C9o

utof

planedeform

ation)

7412

8068559

0783

7377

5395416

1452

120574(N2minus

Hw

agging)+120574(r

ingO4N1N2C10

O5N2C8C9o

utof

planedeform

ation)

689145

1874

44013

6897

4533709

6088

120588(CH2C12)+](N1minus

C11 )+120575(rin

gN2C10N1b

ending)

673146

41930

1197

668088

2271

6203

120574(N2minus

Hw

agging)

6673

0512

192541

654352

93406

1226

120588(CH2C11)+120575(rin


ending)

563675

9497

2281

563724

1131

65625

120575(NCC

N1C11C12

bend

ing)+120588(C

H2C12)

5014

5814

9096

74503295

3892

19791

120575(CCOC11C12O6b

ending)+120575(

ringC8C7N1O4C10N2b

ending)

436878

83784

2489

435560

35623

7042

120574(O6minus

Hw

agging)+120575(

ringN2C10N1C11N1C7b

ending)

408328

1272

9013

8440

9922

9849

1315

120574(O6minus

Hw

agging)+120574(

ringC8C7N1C10

outo

fplanedeform

ation)

alim

itedto

thedescrip

tionof

stron

gvibrationalm

odes

ofthestu

died

moleculeandtherepo

rted

vibrationalm

odes

arethoseof

thestu

died

moleculein

gasp

hase

althou

ghmanydescrip

tions

areidenticalin

the

twomedia(in

gasa

ndwater)

b]] sand

] asstr

etching(sim

plesymmetric

and

asym

metric

)120575inplaneb

ending

(sim

plesciss

oring)120574out

ofplaneb

ending

(twistingovertonew

agging

deformation)120588

rocking


0 500 1000 1500 2000 2500 3000 3500 4000

0

500

1000

1500

2000

2500

IR In

tens

ity (K

mm

ol)


0 500 1000 1500 2000 2500 3000 3500 40000

50

100

150

200

250

300

350

400

450

500



Ram

an A

ctiv

ity (

4A

MU

)









HOMO (-7122 eV) LUMO (-1955 eV)











0 1 2 3 4 5

0

1

2

3

Energy (eV)


5167 eV







4 Conclusions


0m and S0m




Data Availability




Acknowledgments




References



























































Shock and Vibration





Volume 2018














Geophysics



Volume 2018




Volume 2018






Journal of

Chemistry




RotatingMachinery







ency

(cmminus1)IR

intensity

(Kmm

ol)Ra

man

activ

ity(A4A

MU)andassig

nmentsof

thestu

died

moleculeat

B3LY

P6-31+G

(d)levelin

gasp

hase

andaqueou

ssolutio

nGas

phase

Aqueou

ssolution

ASSIG

NMEN

TSab

Frequency

IRintensity

Raman

activ

ityFrequency

IRIntensity

Raman

activ

ity3693369

69061

44508

3705977

87657

9819

2](06minus

H)

3586430

75248

74241

3577938

115905

1495

67](N2minus

H)

3238231

2895

77440

3251219

6661

182559

](C7minus

H)

3141099

6603

4217

33160

495

8380

10664

1] a

s(CH2C11

andC12)

3084940

3319

7113

127

3111124

43204

166701

] s(C

H2C11)+]

as(C

H2C12)

308112

423687

97655

3104

464

21819

312681

] s(C

H2C11)+]

as(C

H2C12)

3000

562

7415

1202427

3031451

86618

368806

] s(C

H2C12)

178916

9538145

9916

21740

087

4217

501273

85] (C=0C9a


H)

1762630

7173

545220

1707784

1468833

235994

] (C10=O)+120575(N2minus

H)

1711453

1010

795119

7169917

1818283

54809

] (C7=

C8)+120575(C7minus

H)

1529037

1166

9056

1519870

1880

16642

120575(CH2C12

sciss

oring)

1500

104

20636

1317

81496912

43736

27878

120575(CH2C11

sciss

oring)

1482282

55577

3273

1489073

93803

1353

0](r

ingCminusC

andCminusN


twisting)

144819

045498

9248

1443952

60681

26451

120575 (O6minus

H)+120574(C

H2C12

overtone)

1427302

23576

7779

1427587

30543

20827

120575 (N2minus

H)+120574(C

H2C12

overtone)

1421510

3616

1511

1423682

23509

6940

120575 (N2minus

HC7minus

H)+120574(C

H2C11

overtone)

1390505

118205

7611

138718

1119

856

11122

120574(CminusHC11


H)

1380598

3819

640

217

1380309

114269

1316

49120575 (O6minus

HC7minus

H )+120574(C

H2C11

twisting)

1347554

8316

479

091349457

1297

4913904

120575 (O6minus

HC7minus

HN2minus


andC12)

1281458

4432

317485

1284076

103003

28210

120574(CH2C12


1256870

106831

7770

1240

649

71580

4513

9] (C8minus

FN2minus

C10 )+120575(C7minusH)+120574(C

H2C12

twisting)

1225483

75439

2778

1231243

282155

6081

120574(CH2C11

and

C12t


HC7minus

HN2minus

H)

11712

7571265

6885

1178572

74246

37119

](ringCminusN


HC7minus

HN2minus


andC12)

1152566

18908

10654

1144897

77474

17510


HC7minus

H)+120574 (CminusHC11 )

111400

040

616

3788

1092868

41455

9179


H)

1078303

39558

0562

1065832

1210

3817

64120575 (O6minus

H)+120588(C

H2C11

and

C12)

950975

14994

4003

9574

2426819

6760


HC7minus

H)

9019

4924808

3319

926124

3339

48721

120574(C7minus

H)

888823

16915

2971

888838

38112

6208

120575 (N2minus

HC7minus

H)+120588(

CH2C11

and

C12)+](C11minus

C12 )

856699

1215

76746

85646

428472

12028

120575 (N2minus

H)+120588(

CH2C11)+](C11minus

C12 )

7775

9711367

16247

782228

10639

48556

120575(rin

gCNC

NCN

bend

ing)

7518

940787

0694

752374

0591

2834


O5N2C8C9o

utof

planedeform

ation)

7412

8068559

0783

7377

5395416

1452

120574(N2minus

Hw

agging)+120574(r

ingO4N1N2C10

O5N2C8C9o

utof

planedeform

ation)

689145

1874

44013

6897

4533709

6088

120588(CH2C12)+](N1minus

C11 )+120575(rin

gN2C10N1b

ending)

673146

41930

1197

668088

2271

6203

120574(N2minus

Hw

agging)

6673

0512

192541

654352

93406

1226

120588(CH2C11)+120575(rin


ending)

563675

9497

2281

563724

1131

65625

120575(NCC

N1C11C12

bend

ing)+120588(C

H2C12)

5014

5814

9096

74503295

3892

19791

120575(CCOC11C12O6b

ending)+120575(

ringC8C7N1O4C10N2b

ending)

436878

83784

2489

435560

35623

7042

120574(O6minus

Hw

agging)+120575(

ringN2C10N1C11N1C7b

ending)

408328

1272

9013

8440

9922

9849

1315

120574(O6minus

Hw

agging)+120574(

ringC8C7N1C10

outo

fplanedeform

ation)

alim

itedto

thedescrip

tionof

stron

gvibrationalm

odes

ofthestu

died

moleculeandtherepo

rted

vibrationalm

odes

arethoseof

thestu

died

moleculein

gasp

hase

althou

ghmanydescrip

tions

areidenticalin

the

twomedia(in

gasa

ndwater)

b]] sand

] asstr

etching(sim

plesymmetric

and

asym

metric

)120575inplaneb

ending

(sim

plesciss

oring)120574out

ofplaneb

ending

(twistingovertonew

agging

deformation)120588

rocking


0 500 1000 1500 2000 2500 3000 3500 4000

0

500

1000

1500

2000

2500

IR In

tens

ity (K

mm

ol)


0 500 1000 1500 2000 2500 3000 3500 40000

50

100

150

200

250

300

350

400

450

500



Ram

an A

ctiv

ity (

4A

MU

)









HOMO (-7122 eV) LUMO (-1955 eV)











0 1 2 3 4 5

0

1

2

3

Energy (eV)


5167 eV







4 Conclusions


0m and S0m




Data Availability




Acknowledgments




References



























































Shock and Vibration





Volume 2018














Geophysics



Volume 2018




Volume 2018






Journal of

Chemistry




RotatingMachinery






0 500 1000 1500 2000 2500 3000 3500 4000

0

500

1000

1500

2000

2500

IR In

tens

ity (K

mm

ol)


0 500 1000 1500 2000 2500 3000 3500 40000

50

100

150

200

250

300

350

400

450

500



Ram

an A

ctiv

ity (

4A

MU

)









HOMO (-7122 eV) LUMO (-1955 eV)











0 1 2 3 4 5

0

1

2

3

Energy (eV)


5167 eV







4 Conclusions


0m and S0m




Data Availability




Acknowledgments




References



























































Shock and Vibration





Volume 2018














Geophysics



Volume 2018




Volume 2018






Journal of

Chemistry




RotatingMachinery






HOMO (-7122 eV) LUMO (-1955 eV)











0 1 2 3 4 5

0

1

2

3

Energy (eV)


5167 eV







4 Conclusions


0m and S0m




Data Availability




Acknowledgments




References



























































Shock and Vibration





Volume 2018














Geophysics



Volume 2018




Volume 2018






Journal of

Chemistry




RotatingMachinery






0 1 2 3 4 5

0

1

2

3

Energy (eV)


5167 eV







4 Conclusions


0m and S0m




Data Availability




Acknowledgments




References



























































Shock and Vibration





Volume 2018














Geophysics



Volume 2018




Volume 2018






Journal of

Chemistry




RotatingMachinery







Data Availability




Acknowledgments




References



























































Shock and Vibration





Volume 2018














Geophysics



Volume 2018




Volume 2018






Journal of

Chemistry




RotatingMachinery
















































Shock and Vibration





Volume 2018














Geophysics



Volume 2018




Volume 2018






Journal of

Chemistry




RotatingMachinery

















Shock and Vibration





Volume 2018














Geophysics



Volume 2018




Volume 2018






Journal of

Chemistry




RotatingMachinery








Shock and Vibration





Volume 2018














Geophysics



Volume 2018




Volume 2018






Journal of

Chemistry




RotatingMachinery





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