Embed Size (px)
Citation preview
CHARACTERIZATION of the SiC3H- anion
N. Inostroza1, M. L. Senent1 1 Instituto de Estructura de la Materia, C.S.I.C,
Departamento de Astrofísica Molecular e Infrarroja, , Serrano 121 Madrid 28006,España.2
Columbus, Ohio21-25 June, 2010
The 65th International Symposium on Molecular Spectroscopy
Silicon Carbon Chains: Relevance
1) Material ChemistryChemistry: Silicon carbon molecules are components of many semiconductor
devices.
Laboratory detection of small silicon carbon molecules (McCarthy et.al 2003)
2) Molecular Astrophysics: Silicon carbon molecules have been identified in gas phase. (Si is a major constituent of interstellar dust but exist in gas phase)
SiC3 / C4
SiC3H- isovalent to C4H-
N.Inostroza, et.al. A&A (2008),
C4H- has been one of the first anions detected. Cernicharo, J. et.al, ApJ. 2002
Neutral C4H was detected 20 years
early.
The hydrogen-bearing silicon carbide radicals SiCnH are isovalent to Cn+1H species.
SiC3H-
neutral anion Ea
CSi (X3) 0.8831 l-CSi- (X2+) 11.5921 2.42
c-C2Si (X1A1) 2.9587 l-C2Si- (X2) 5.6931 1.41
c-C3Si (X1A1) 3.8671l-C3Si- (X2) 2.4308
2.492.89l-C3Si (X3-) 4.4016
l-C4Si (X1+) 6.2111 l-C4Si- (X2) 2.2349 2.31
l-C5Si (X3-) 6.4927 l-C5Si- (X2) 5.2765 3.30
l-SiCH (X2) 0.5771 l-SiCH- (X1+) 12.3875 3.88
l-SiC2H (X2) 1.1201 l-SiC2H- (X3-) 1.3651 1.32
l-SiC3H (X2) 1.1074 l-SiC3H- (X1+) 9.3023 2.70
l-SiC4H (X2) 1.3061 l-SiC4H- (X3-) 10.8913 1.69
l-SiC5H (X2) 0.5122 l-SiC5H- (X1+) 4.8991 2.98
neutral anion Ea
CSi (X3) 0.8831 l-CSi- (X2+) 11.5921 2.42
c-C2Si (X1A1) 2.9587 l-C2Si- (X2) 5.6931 1.41
c-C3Si (X1A1) 3.8671l-C3Si- (X2) 2.4308
2.492.89l-C3Si (X3-) 4.4016
l-C4Si (X1+) 6.2111 l-C4Si- (X2) 2.2349 2.31
l-C5Si (X3-) 6.4927 l-C5Si- (X2) 5.2765 3.30
l-SiCH (X2) 0.5771 l-SiCH- (X1+) 12.3875 3.88
l-SiC2H (X2) 1.1201 l-SiC2H- (X3-) 1.3651 1.32
l-SiC3H (X2) 1.1074 l-SiC3H- (X1+) 9.3023 2.70
l-SiC4H (X2) 1.3061 l-SiC4H- (X3-) 10.8913 1.69
l-SiC5H (X2) 0.5122 l-SiC5H- (X1+) 4.8991 2.98
neutral anion Ea
CSi (X3) 0.8831 l-CSi- (X2+) 11.5921 2.42
c-C2Si (X1A1) 2.9587 l-C2Si- (X2) 5.6931 1.41
c-C3Si (X1A1) 3.8671l-C3Si- (X2) 2.4308
2.492.89l-C3Si (X3-) 4.4016
l-C4Si (X1+) 6.2111 l-C4Si- (X2) 2.2349 2.31
l-C5Si (X3-) 6.4927 l-C5Si- (X2) 5.2765 3.30
l-SiCH (X2) 0.5771 l-SiCH- (X1+) 12.3875 3.88
l-SiC2H (X2) 1.1201 l-SiC2H- (X3-) 1.3651 1.32
l-SiC3H (X2) 1.1074 l-SiC3H- (X1+) 9.3023 2.70
l-SiC4H (X2) 1.3061 l-SiC4H- (X3-) 10.8913 1.69
l-SiC5H (X2) 0.5122 l-SiC5H- (X1+) 4.8991 2.98
neutral anion Ea
CSi (X3) 0.8831 l-CSi- (X2+) 11.5921 2.42
c-C2Si (X1A1) 2.9587 l-C2Si- (X2) 5.6931 1.41
c-C3Si (X1A1) 3.8671l-C3Si- (X2) 2.4308
2.492.89l-C3Si (X3-) 4.4016
l-C4Si (X1+) 6.2111 l-C4Si- (X2) 2.2349 2.31
l-C5Si (X3-) 6.4927 l-C5Si- (X2) 5.2765 3.30
l-SiCH (X2) 0.5771 l-SiCH- (X1+) 12.3875 3.88
l-SiC2H (X2) 1.1201 l-SiC2H- (X3-) 1.3651 1.32
l-SiC3H (X2) 1.1074 l-SiC3H- (X1+) 9.3023 2.70
l-SiC4H (X2) 1.3061 l-SiC4H- (X3-) 10.8913 1.69
l-SiC5H (X2) 0.5122 l-SiC5H- (X1+) 4.8991 2.98
neutral anion Ea
CSi (X3) 0.8831 l-CSi- (X2+) 11.5921 2.42
c-C2Si (X1A1) 2.9587 l-C2Si- (X2) 5.6931 1.41
c-C3Si (X1A1) 3.8671l-C3Si- (X2) 2.4308
2.492.89l-C3Si (X3-) 4.4016
l-C4Si (X1+) 6.2111 l-C4Si- (X2) 2.2349 2.31
l-C5Si (X3-) 6.4927 l-C5Si- (X2) 5.2765 3.30
l-SiCH (X2) 0.5771 l-SiCH- (X1+) 12.3875 3.88
l-SiC2H (X2) 1.1201 l-SiC2H- (X3-) 1.3651 1.32
l-SiC3H (X2) 1.1074 l-SiC3H- (X1+) 9.3023 2.70
l-SiC4H (X2) 1.3061 l-SiC4H- (X3-) 10.8913 1.69
l-SiC5H (X2) 0.5122 l-SiC5H- (X1+) 4.8991 2.98
neutral anion Ea
CSi (X3) 0.8831 l-CSi- (X2+) 11.5921 2.42
c-C2Si (X1A1) 2.9587 l-C2Si- (X2) 5.6931 1.41
c-C3Si (X1A1) 3.8671l-C3Si- (X2) 2.4308
2.492.89l-C3Si (X3-) 4.4016
l-C4Si (X1+) 6.2111 l-C4Si- (X2) 2.2349 2.31
l-C5Si (X3-) 6.4927 l-C5Si- (X2) 5.2765 3.30
l-SiCH (X2) 0.5771 l-SiCH- (X1+) 12.3875 3.88
l-SiC2H (X2) 1.1201 l-SiC2H- (X3-) 1.3651 1.32
l-SiC3H (X2) 1.1074 l-SiC3H- (X1+) 9.3023 2.70
l-SiC4H (X2) 1.3061 l-SiC4H- (X3-) 10.8913 1.69
l-SiC5H (X2) 0.5122 l-SiC5H- (X1+) 4.8991 2.98
Ea RCCSD(T)-F12A/aug-cc-pVTZ
neutral anion Ea
CSi (X3) 0.8831 l-CSi- (X2+) 11.5921 2.42
c-C2Si (X1A1) 2.9587 l-C2Si- (X2) 5.6931 1.41
c-C3Si (X1A1) 3.8671l-C3Si- (X2) 2.4308
2.492.89l-C3Si (X3-) 4.4016
l-C4Si (X1+) 6.2111 l-C4Si- (X2) 2.2349 2.31
l-C5Si (X3-) 6.4927 l-C5Si- (X2) 5.2765 3.30
l-SiCH (X2) 0.5771 l-SiCH- (X1+) 12.3875 3.88
l-SiC2H (X2) 1.1201 l-SiC2H- (X3-) 1.3651 1.32
l-SiC3H (X2) 1.1074 l-SiC3H- (X1+) 9.3023 2.70
l-SiC4H (X2) 1.3061 l-SiC4H- (X3-) 10.8913 1.69
l-SiC5H (X2) 0.5122 l-SiC5H- (X1+) 4.8991 2.98
neutral anion Ea
CSi (X3) 0.8831 l-CSi- (X2+) 11.5921 2.42
c-C2Si (X1A1) 2.9587 l-C2Si- (X2) 5.6931 1.41
c-C3Si (X1A1) 3.8671l-C3Si- (X2) 2.4308
2.492.89l-C3Si (X3-) 4.4016
l-C4Si (X1+) 6.2111 l-C4Si- (X2) 2.2349 2.31
l-C5Si (X3-) 6.4927 l-C5Si- (X2) 5.2765 3.30
l-SiCH (X2) 0.5771 l-SiCH- (X1+) 12.3875 3.88
l-SiC2H (X2) 1.1201 l-SiC2H- (X3-) 1.3651 1.32
l-SiC3H (X2) 1.1074 l-SiC3H- (X1+) 9.3023 2.70
l-SiC4H (X2) 1.3061 l-SiC4H- (X3-) 10.8913 1.69
l-SiC5H (X2) 0.5122 l-SiC5H- (X1+) 4.8991 2.98
CASSCF/aug-cc-pVTZ
neutral anion Ea
CSi (X3) 0.8831 l-CSi- (X2+) 11.5921 2.42
c-C2Si (X1A1) 2.9587 l-C2Si- (X2) 5.6931 1.41
c-C3Si (X1A1) 3.8671l-C3Si- (X2) 2.4308
2.492.89l-C3Si (X3-) 4.4016
l-C4Si (X1+) 6.2111 l-C4Si- (X2) 2.2349 2.31
l-C5Si (X3-) 6.4927 l-C5Si- (X2) 5.2765 3.30
l-SiCH (X2) 0.5771 l-SiCH- (X1+) 12.3875 3.88
l-SiC2H (X2) 1.1201 l-SiC2H- (X3-) 1.3651 1.32
l-SiC3H (X2) 1.1074 l-SiC3H- (X1+) 9.3023 2.70
l-SiC4H (X2) 1.3061 l-SiC4H- (X3-) 10.8913 1.69
l-SiC5H (X2) 0.5122 l-SiC5H- (X1+) 4.8991 2.98
CASSCF/aug-cc-pVTZ
neutral anion Ea
CSi (X3) 0.8831 l-CSi- (X2+) 11.5921 2.42
c-C2Si (X1A1) 2.9587 l-C2Si- (X2) 5.6931 1.41
c-C3Si (X1A1) 3.8671l-C3Si- (X2) 2.4308
2.492.89l-C3Si (X3-) 4.4016
l-C4Si (X1+) 6.2111 l-C4Si- (X2) 2.2349 2.31
l-C5Si (X3-) 6.4927 l-C5Si- (X2) 5.2765 3.30
l-SiCH (X2) 0.5771 l-SiCH- (X1+) 12.3875 3.88
l-SiC2H (X2) 1.1201 l-SiC2H- (X3-) 1.3651 1.32
l-SiC3H (X2) 1.1074 l-SiC3H- (X1+) 9.3023 2.70
l-SiC4H (X2) 1.3061 l-SiC4H- (X3-) 10.8913 1.69
l-SiC5H (X2) 0.5122 l-SiC5H- (X1+) 4.8991 2.98
C4H-
C2H-
C6H-
neutral anion Ea
CSi (X3) 0.8831 l-CSi- (X2+) 11.5921 2.42
c-C2Si (X1A1) 2.9587 l-C2Si- (X2) 5.6931 1.41
c-C3Si (X1A1) 3.8671l-C3Si- (X2) 2.4308
2.492.89l-C3Si (X3-) 4.4016
l-C4Si (X1+) 6.2111 l-C4Si- (X2) 2.2349 2.31
l-C5Si (X3-) 6.4927 l-C5Si- (X2) 5.2765 3.30
l-SiCH (X2) 0.5771 l-SiCH- (X1+) 12.3875 3.88
l-SiC2H (X2) 1.1201 l-SiC2H- (X3-) 1.3651 1.32
l-SiC3H (X2) 1.1074 l-SiC3H- (X1+) 9.3023 2.70
l-SiC4H (X2) 1.3061 l-SiC4H- (X3-) 10.8913 1.69
l-SiC5H (X2) 0.5122 l-SiC5H- (X1+) 4.8991 2.98
C4H-
Isomers of SiCIsomers of SiC33HH--
l-SiC3H-
X1+
c-SiC3H-
X1A’
l1-SiC3H-
X1A’
c1-SiC3H-
X1A’
c3-SiC3H-
X1A’
l2-SiC3H -
X1A’
c4-SiC3H-
X1A
c5-SiC3H-
X1A’
c6-SiC3H-
X1A’
c7-SiC3H-
X1A’
l3-SiC3H-
X1A’
c2-SiC3H-
X1A’
Isomers of SiCIsomers of SiC33HH--
l-SiC3H-
X1+
c-SiC3H-
X1A’
l1-SiC3H-
X1A’
c1-SiC3H-
X1A’
c3-SiC3H-
X1A’
l2-SiC3H -
X1A’
c4-SiC3H-
X1A
c5-SiC3H-
X1A’
c6-SiC3H-
X1A’
c7-SiC3H-
X1A’
l3-SiC3H-
X1A’
c2-SiC3H-
X1A’
Isomers of SiCIsomers of SiC33HH--
l-SiC3H-
X1+ Er=0.0
c-SiC3H-
X1A’ Er=1.15
l1-SiC3H-
X1A’ Er=1.70
c1-SiC3H-
X1A’ Er=1.86
c3-SiC3H-
X1A’ Er=1.92
l2-SiC3H -
X1A’ Er=2.04
c4-SiC3H-
X1A Er=2.06
c5-SiC3H-
X1A’ Er=2.14
c6-SiC3H-
X1A’Er=2.43
c7-SiC3H-
X1A’ Er=2.63
l3-SiC3H-
X1A’ Er=2.80
c2-SiC3H-
X1A’ Er=1.92
RCCSD(T)/CASSCFaug-cc-pVTZ
Isomers of SiCIsomers of SiC33HH--
c-SiC3H-
X1A’ Er=1.15
l1-SiC3H-
X1A’ Er=1.70
c1-SiC3H-
X1A’ Er=1.86
RCCSD(T)/CASSCFaug-cc-pVTZ
c3-SiC3H-
X1A’ Er=1.92
l2-SiC3H -
X1A’ Er=2.04
c4-SiC3H-
X1A Er=2.06
c5-SiC3H-
X1A’ Er=2.14
c6-SiC3H-
X1A’Er=2.43
c7-SiC3H-
X1A’ Er=2.63
l3-SiC3H-
X1A’ Er=2.80
c2-SiC3H-
X1A’ Er=1.92
Basis set na l-SiC3H-
Be
l-SiC3D-
Be
RCCSD(T)-F12Aaug-cc-pVTZ
8 2598.33 2438.24
aug-cc-pVTZ 8 2578.13 2419.55aug-cc-pVQZ 8 2594.03 2434.29aug-cc-pV5Z 8 2599.57 2439.36
CBSb 2605.16 2444.36aug-cc-pCVQZ 4 2603.00 2442.46aug-cc-pCVQZ 1 2611.51 2450.45
a) n=number of frozen core orbitalsb) CBS =complete basis set (aug-cc-pVZ)2 4 6 8 10 12 14
2575
2580
2585
2590
2595
2600
2605
aug-cc-pVXZ
Be(MHz)
= 13.59 Debyes = 13.59 Debyes CASSCF/aug-cc-pV5ZCASSCF/aug-cc-pV5Z
Becore 17 MHz Bvib 2 MHz
BB0 0 ((ll-SiC-SiC33HH
--)=2620.74 MHz)=2620.74 MHz
Becore
= Be(aug-cc-pCVQZ, n=1) - Be(aug-cc-pVQZ, n=8)
B0 = BeCBS + Be
core + Bvib
Be=BeCBS + Be
1 (X+1)-3 + Be2 (X+1)-5 + ……
BB0 0 ( (ll-SiC-SiC33DD
--)= 2459.81 MHz)= 2459.81 MHz
Dipole moment and rotational constant
Vertical excitation energies of l-SiC3H-
Sym ErMRCI
Sym EMRCI
X2 0.0b 1+ 0.0d
2+ 2.01 1 3.092 5.66 1 3.292- 5.43 1- 3.224+ 3.43 3+ 2.484 3.82 3 3.104- 4.19 3 2.664 2.21 3- 2.85
MRCI/aug-cc-pVTZ
c) Ea=-493.205588 a.u.; d) Ea=-403.597248 a.u.
Ea= 2.70 eV
Vertical excitation energies of l-SiC3H-
Sym ErMRCI
Sym EMRCI
X2 0.0b 1+ 0.0d
2+ 2.01 1 3.092 5.66 1 3.292- 5.43 1- 3.224+ 3.43 3+ 2.484 3.82 3 3.104- 4.19 3 2.664 2.21 3- 2.85
MRCI/aug-cc-pVTZ
c) Ea=-493.205588 a.u.; d) Ea=-403.597248 a.u.
Ea= 2.70 eV
Vertical excitation energies of l-SiC3H-
Sym ErMRCI
Sym EMRCI
X2 0.0b 1+ 0.0d
2+ 2.01 1 3.092 5.66 1 3.292- 5.43 1- 3.224+ 3.43 3+ 2.484 3.82 3 3.104- 4.19 3 2.664 2.21 3- 2.85
MRCI/aug-cc-pVTZ
c) Ea=-493.205588 a.u.; d) Ea=-403.597248 a.u.
Ea= 2.70 eV
Potential Energy Surface PESPotential Energy Surface PES
Definition of linear angles (Hoy et. al Mol.Phys.1972)
RCCSD(T)-F12/ cc-pVTZ-F12
GRID 1409 geometries :Bond distances Rref+0.03 Å ≥ R ≥ Rref-0.03ÅTorsional angles re f + 5.0o ≥ ≥ re f – 5.0° Planar bending angles=+5.0ºFITR2=1.0, =0.4 cm-1
Spectroscopic ParametersSpectroscopic Parameters
Spectroscopic ParametersSpectroscopic Parameters
Spectroscopic ParametersSpectroscopic Parameters
Spectroscopic ParametersSpectroscopic Parameters
Spectroscopic ParametersSpectroscopic Parameters
Spectroscopic ParametersSpectroscopic Parameters
Spectroscopic ParametersSpectroscopic Parameters
Spectroscopic ParametersSpectroscopic Parameters
Conclusions
The formation of SiC3H- seems to be viable on the basis of our calculations
B0=2620.74 MHz = 13.59 Debyes = 13.59 Debyes
We hope that the future astronomical observatory ALMA will find our molecule
SiC3H is strongly stabilized by electron attachment
ACKNOWLEGMENTS
The authors acknowledge the Ministerio de Ciencia e Innovación of SPAIN for grants (AYA2008-00446 and AYA2009-05801-E/AYA) and also to CESGA for computing facilities.
Thank you for your attention !Thank you for your attention !
![Monografies del Fons Millàs, d'altres autors · Millás Vallicrosa y David Romano Publicació: Madrid [etc.] : C.S.I.C. Instituto Arias Montano, 1954 Localització: Ciència i Tecnol-](https://img.pdfslide.us/doc/110x75/61213b6b18b5c15f605ed85f/monografies-del-fons-mills-daltres-autors-mills-vallicrosa-y-david-romano.jpg)
