23rd Winter School inTheoretical Chemistry

Actinide Chemistry

Department of ChemistryUniversity of Helsinki

Finland

December 10-14 2007

Supported by the Theoretical User Lab (ThUL) a part of Actinet

Programme

Monday 10.12 Tuesday 11.12 Wednesday 12.12

Thursday 13.12

Friday 14.12

09.15

10.0010.15 Welcome

Gibson Dolg Grenthe Roos

Break Break Break Break

10.30 Kaltsoyannis Visscher Visscher Panak Rösch

11.15 Kaltsoyannis Visscher Visscher Panak Discussion

12.00 Lunch Lunch Lunch Lunch Lunch

13.15 Cummins Cummins

14.00 Cummins Cummins

14.45 Break Break

15.15 Barandarian Andrews

16.00 Pitzer Andrews

16.45 Break Break

17.00

19.00

Div. Of Comp. Chem.Meeting

(in Swedish)Poster Session

Free Afternoon

Lehto

Dognon

Break

Conradson

ValletDeparture

Key Lectures

Kit Cummins, MIT (4 h):

• ''Preliminary title: Organometallic chemistry of the actinides''

Nik Kaltsoyannis, University College London (2 h):

• ''A lack of synergy? An unusual actinide-ligand bonding mode''

• ''Nitrogen-based analogues of the uranyl ion''

Petra Panak, INE Karlsruhe (2 h):

• ''Combined TRLFS, EXAFS and theoretical investigations on actininde/lanthanide complexed with partioning relevant N-Donor ligands''

Luuk Visscher, VU Amsterdam (4 h):

• ''Quantum chemistry methods for heavy element chemistry''

Lectures

L. Andrews, University of Virginia (1 h):

• ''Actinide Metal Atom (Th and U) Reactions to Form Novel Molecules''

Z. Barandiaran, UA Madrid (1 h):

• ''Structure, bonding, and spectroscopy of actinides in crystals. A quantum chemical perspective.''

S. Conradson, Los Alamos National Laboratory (1 h):

• ''Addressing the Structural Chemistry of UO2+x and PuO2+x with Laboratory and Computer Experiments''

J.-P. Dognon, Commissariat à l'Énergie Atomique (1 h):

• ''Lanthanide and actinide theoretical chemistry : from atomic clusters to condensed phase''

M. Dolg, University of Cologne (1 h):

• ''Energy-consistent pseudopotentials: new developments for actinides''

J. Gibson, Lawrence Berkeley National Laboratory (1 h):

• ''Fundamental aspects of 5f-element chemistry revealed by gas-phase reactions of actinide ions''

I. Grenthe, KTH Stockholm (1 h):

• ''Solution coordination chemistry; stoichiometry and structre, thermodynamics and dynamics - the reciprocity of experiment and theory''

J. Lehto, University of Helsinki (1 h):

• ''Analysis of transuranium elements in the environment''

R. M. Pitzer, Ohio State University (1 h):

• ''Multireference Spin-Orbit Configuration Interaction with Columbus; Application to the Electronic Spectrum of UO2+''

B. Roos, Lund University (1 h):

• ''Multiconfigurational quantum chemistry--the state of the art''

N. Rösch, Technische Universität München (1 h):

• ''Density functional modeling of uranyl sorption at mineral-water interfaces''

V. Vallet, l'Université de Lille (1 h):

• ''How to probe the coordination chemistry and electronic spectroscopy of actinide compounds? DFT versus standard ab initio methods.''

Posters

Efficient Two-component Hartree-Fock and Density Functional Methods

M. K. Armbruster, F. Weigend*, W. Klopper**Forschungszentrum Karlsruhe, Institut für Nukleare Entsorgung, Postfach 3640, D-76021 Karlsruhe(*) Forschungszentrum Karlsruhe, Institut für Nanotechnologie, Postfach 3640, D-76021 Karlsruhe

(**) Center for Functional Nanostructures (CFN) and Institut für Physikalische Chemie, Universität Karlsruhe, D-76128 Karlsruhe

Efficient self-consistent field (SCF) schemes including both scalar relativistic effects and spin-orbit (SO) interactions at Hartree-Fock (HF) and density functional (DFT) level are presented. SO interactions require the extension of standard procedures to two-component formalisms. Efficiency is achieved by using effective core potentials (ECPs) and by employing the resolution-of-the-identity (RI) approximation for the Coulomb part (RI-J) in pure DFT calculations as well as also for the HF-exchange part (RI-JK) in case of HF or hybrid-DFT treatments. The procedure were implemented in the program system TURBOMOLE, efficiency is demonstrated for comparably large systems, such as Pb54 . Relevance of SO effects for electronic structure and stability is illustrated by treatments of small Tl, Pb, Bi and Po clusters with and without accounting for SO effects.

Analysis of bond characters in diatomic chalcogenides and triatomic halides

Pekka Pyykkö and Michiko Atsumi

Presenting author: Michiko Atsumi

A chemical bond is the mechanism, responsible for the attractive interactions between atoms and molecules. Recently there has been much interest in multiple bonding between atoms in a molecule. Theoretical and experimental work have challenged old chemical paradigms concerning the possible multiplicity that can be achieved in a chemical bond. The only elements without triple bonds in [1] were the alkali metals, the Group 12 metals Zn-Hg, and the lightest noble gases He, Ne. The elements of group 12 form halide complexes MX2 (M=Zn, Cd, Hg; X=F, Cl, Br, I ) in which their oxidation states are no higher than 2+. Mercury has many unique properties within its group, and some of its chemistry is very different from zinc and cadmium. They have not been studied yet systematically using multiconfigrational quantum chemical methods. Here, natural bond orders (NBO) [2] and effective bond orders (EBO) [3] are used to study the bonding.

References[1] P.Pyykkö, S.Riedel, M.Patzschke, Chem. Eur.J. 2005, 11, 3511-3520[2] E.D.Grendening, F.Weinhold, J. Comp. Chem. 1998, 19, 610-627[3] B.O.Roos, A.C.Borin, L.Gagliardi, Angew.Chem.Int.Ed. 2007, 46, 1469-1472

Department of Chemistry, University of Helsinki, Finland

Example Abstract

THEORETICAL STUDY OF THE SPECTROSCOPY OF PROTACTINIUM(IV) IN AQUEOUS SOLUTION

R. Belmecheri1,2), V. Vallet2), J.-P. Flament2), B. Schimmelpfenning3), C.M. Marquardt3), P. Panak3), R.

Klenze3)

1) Université des Sciences et Technologie de Houarie Boumediene, Laboratoire de Thermodynamique et de Modelisation Moléculaire, Algers, Algeria

2) Université des Sciences et Technologies de Lille 1, Laboratoire PhLAM, CNRS UMR8523, 59655 Villeneuve d’Ascq Cedex, France

3) Institut für Nukleare Entsorgung, Forschungszentrum Karlsruhe, Postfach 3640, D-76021 Karlsruhe, Germany

Time-resolved fluorescence spectroscopy experiments have shown that the Pa(IV) ion has very intense fluorescence band in aquatic solution due to the f1-d1 transitions [1]. The influence of complexation of the absorption and fluorescence spectra has been investigated [2]. The absorption bands are red shifted with increasing fluoride complexation, while no shift is observed in the 469 nm fluorescence band. In hydrolysis conditions, one observed a significant blue shift of the fluorescence band, while the absorption band is only slightly red shifted. These experimental observations raise the question of the nature and the position of the 5f and 6d levels for the Pa4+ in solution. We have used quantum chemical methods to answer two questions:

1. the structure and coordination of Pa4+ in solution. We have thus investigated the number of coordinated water molecules in the aqua Pa4+ ion. We also investigate the changes in the first coordination shell upon fluoride and hydroxide complexation.

2. We have used high-level quantum chemical methods to compute the energy levels of the solvated Pa4+ ion and to characterize the absorbing and fluorescing levels. This work is a first step towards the understanding of speciation-dependant spectroscopic properties of actinide ions.

[1] C. M. Marquardt, P.J. Panak, C. Apostolidis, A. Morgenstern, C. Walther, R. Klenze, T. Fanghänel, Radiochim. Acta 92, 1-3 (2004). [2] C. M. Marquardt, P.J. Panak, C. Walther, R. Klenze, Th. Fanghänel, manuscript.

On Relativistic Effects in Zn2 , Cd2 ,Hg2, HgHe and HgXe Dimers, a CCSD(T) Study.

Lukas Bucinsky, Stanislav Biskupic, Vladimir Lukes, Michal Ilcin*

Presenting author: Lukas Bucinsky

We present a study on relativistic effects in weakly bounded dimers. The relativistic effects are gained from comparing CCSD(T) ground potential curves at different levels of Hamiltonian. Calculations at the Dirac-Coulomb Hamiltonian (DCH), the 4-component spin-free Hamiltonian (SF) [1] and the non-relativistic Levy-Leblond Hamiltonian [2] are presented; the DIRAC04 [3] software suite is used. The ground state potential curves are counterpoise corrected [4]. The employed dual family primitive basis sets of DZ [5] and TZ [6] quality are enlarged by diffuse and augmentation Gaussian primitives. The active space is restricted from -1.0 to 5.0 Hartree in the CCSD(T) calculations; only valence electrons and about 200 virtual spinors. The small component ~V small component part of the Fock matrix (FSS) is neglected in DCH and SF CCSD(T) calculations. The results show that the scalar/spin-free relativistic effects are the dominant relativistic correction to the ground state potential curves of studied systems. The relativistic effects are most notably present in the relativistic contraction of equilibrium bond length and changes of binding energies(De). The relativistic corrections to De are in the case of Zn2, Cd2 and Hg2 dimers of antibonding character, contrary to HgHe and HgXe dimers.

References[1] K. G. Dyall, J. Chem. Phys., 100, 2118-2127 (1994)[2] J. M. Lévy-Leblond, Commun. Math. Phys., 6, 286-311 (1967)[3] dirac 04, a relativistic ab initio electronic structure program, Release DIRAC04.0(2004), written by H. J. Aa. Jensen, T. Saue, and L. Visscher with contributionsfrom V. Bakken, E. Eliav, T. Enevoldsen, T. Fleig, O. Fossgaard, T. Helgaker,J. Laerdahl, C. V. Larsen, P. Norman, J. Olsen, M. Pernpointner, J. K. Pedersen,K. Ruud, P. Salek, J. N. P. van Stralen, J. Thyssen, O. Visser, and T. Winther.[4] S. F. Boys, F. Bernadi, Mol. Phys., 19, 553-566 (1970)[5] K. Fægri Jr., Theor. Chem. Acc. 105, 252-258 (2001)[6] K. Fægri Jr., Chem. Phys. 311, 25-34 (2005)

Institute of Physical Chemistry and Chemical Physics, Slovak University of Technology, SK-812 37 Bratislava, Slovak Republic

Implementation of One-Component (Scalar) and Two-Component (Scalar + Spin Orbit Interaction) Douglas Kroll Hess Hamiltonian into the Tonto Software Suite.

Dylan Jayatilaka1, Stanislav Biskupic2, Martin Hudak2, Lukas Bucinsky2

Presenting author: Lukas Bucinsky

Theoretical background of the Douglas Kroll Hess [1, 2, 3] (DKH) Hamiltonian within the second order transformation (DKH2) is presented. The implementation at one-component (scalar) and two-component (scalar + Spin-Orbit interaction) DKH2 level into the Tonto software package [4] is considered. In addition numerical tests of the implemented DKH2 Hamiltonian on closed shell atoms and small molecules containing heavy elements are presented. In future determination of experimental model wave functions from X-ray data [5] and g-tensor calculations [6] should become available at the DKH2 Hamiltonian level in the Tonto software package.

[1] A. Wolf, M. Reiher, B. A. Hess, Relativistic Electronic Structure Theory, Part 1. Fundamentals, editor P. Schwerdtfeger; Elsevier Amsterdam, 2002; Chapter 11 Two-Component Methods and the Generalized Douglas-Kroll Transformation.[2] A. Wolf, M. Reiher, B. A. Hess, J. Chem. Phys. 117 (2002) 9215[3] A. Wolf, M. Reiher, B. A. Hess, Recent Advances in Relativistic Molecular Theory, edited by K. Hirao & Y. Ishikawa; World Scientific 2004; Transgressing Theory Boundaries: The Generalized Douglas-Kroll Transformation [4] D. Jayatilaka, D. J. Grimwood, Tonto: A research tool for quantum chemistry. The University of Western Australia, Nedlands, Western Austarlia, Australia (2000).[5] D. Jayatilaka, D. J. Grimwood, Acta Cryst. A57 (2001) 76 [6] D. Jayatilaka, J. Chem. Phys. 108 (1998) 7587

1Chemistry, School of Biomedical and Chemical Sciences, The University of Western Australia, Crawley 6009, Australia 2Institute of Physical Chemistry and Chemical Physics, Slovak University of Technology, SK-812 37 Bratislava, Slovak Republic

Spectroscopy of U4+ ion in gas phase and in solution

Cécile Danilo,1,2 Valérie Vallet, 1 Jean-Pierre Flament, 1 Ulf Wahlgren2

1 Laboratoire PhLAM, Université des Sciences et Technologies de Lille 1, CNRS UMR 8523, 59655 Villeneuve d’Ascq,

France2 AlbaNova University Center, Stockholm University, Fysikum, S-106 91 Stockholm, Sweden

A two-step effective Hamiltonian-based spin orbit CI method has been used to investigate the

spectroscopy of U4+ in gas phase and in solution. This method treats correlation with the multi-

reference CI or perturbative CASPT2 approaches in the first step and introduces spin-orbit interaction

within an intermediate Hamiltonian scheme in the second step of the calculation.

At the spin free level the results on the naked ion show that the electronic transitions are very

sensitive to the choice of the correlation method and the size of the active space. An important feature

is that perturbative and variational methods give energy transitions in the same range provided that the

6d orbitals are included in the CAS.

At the spin orbit level we examined the influence of the single excitations arising from

different shell orbitals and compared the results with a variation-perturbation approach for the spin

orbit effects. This investigation reveals that a variation-perturbation treatment might be preferable.

The ongoing study concerns also the position of the 5f16d1 states with respect to the 5f2

manifold, which is of importance for the luminescence properties of system containing uranium ions.

We are presently working on the results in gas phase, and plan to determine the 5f16d1 spectrum in

solution in a near future.

For the computation of the spectrum of the solvated species, one can either use a reaction field

to model the solvent or treat the first coordination sphere around the ion explicitly. Both approaches

have been investigated. For the second one, we chose to add eight water molecules rather than nine to

keep a high symmetry system even if [U(H2O)9]4+ is considered the most stable hydrate in aqueous

solution but the effects on the results should be minor. The comparison of the spectra of the solvated

and bare U4+ ion reveals the influence of solvation on the 5f2 manifold. However the interpretation of

the results is limited by the delicate problem of the identification of the states that one faces when

neither J nor Ω is a good quantum number.

Deuteron quadrupole coupling in benzene: Librational corrections and summary

Pekka Pyykkö and Fatemeh Elmi

Presenting author: Fatemeh Elmi

Benzene is the prototype of an aromatic hydrocarbons. As one of the many ways of characterizing its >C-H chemical bond, the quadrupole coupling tensor of the C-D group is of interest. A single-crystal measurement of this deuteron quadrupole coupling constant (DQCC) at 263 K was published in 1966 by Pyykkö and Lähteenmäki. This measurement has never been repeated. In fact, the only other single-crystal value for an aromatic hydrocarbon seems to be a 1967 value for anthracene. It is worthwhile to apply the necessary corrections to the solid-state data, and to summarise the situation. The librational frequencies of solid benzene vary strongly with temperature.In the rigid-molecule model of Bayer , as applied to the present case,the two harmonic librational frequencies of the molecule contribute to the quadrupole interactions. We then consider the measured component $b_{yy}$. The average of the four molecular sites was 93.28(79) kHz. For the two librational frequencies we use the averaged 'U' and 'V' values of 57.28 cm-1 and 82.95 cm-1, respectively, at 273 K. The vibrationally corrected b0 along the y axis becomes (-)97.1(8) kHz. This value is close to the MWFT value for a C6H5D molecule in vacuum and close to the LC NMR results. The MP2 values for an isolated molecule at 300 K are about 3 kHz larger. While the LC results are able to produce a bzz, they are based on a calculated primary C-C distance. Furthermore they could not determine η and used a calculated MP2 value for it, instead. Against this background the agreement of the present, corrected byy value with the others is adequate.

Department of Chemistry, University of Helsinki, P.O.B. 55 (A. I. Virtasen aukio 1), FIN-00014 Helsinki, Finland

Modeling Environment Effects with WFT-in-DFT Embedding

Andre Severo Pereira Gomes,1, ∗ Christoph R. Jacob,1, † and Lucas Visscher1, ‡

1Department of Theoretical Chemistry, Faculty of Sciences, Vrije Universiteit Amsterdam,

De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands

The frozen-density embedding (FDE) scheme, initially developed by Wesolowski and Warshel[1],

is a simple and efficient way of incorporating environment effects into quantum chemical calcula-

tions. Its favorable computational scaling when compared to supermolecule calculation makes

them particularly well suited for calculating these effects on molecular properties[2]. Treating the

non-frozen subsytem at DFT level, however, is not always possible or desirable, either because

DFT is not accurate enough or because one wants to systematically refine the results. In these

cases, one can couple a DFT description of the environment with a wave function (WF) description

of the system of interest, via so-called WF-in-DFT embedding schemes[3].

In this contribution we outline the implementation of a WF-in-DFT procedure employing the

codes ADF, Dalton and DIRAC[4]. As proof-of-concept applications we revisit: (a) the determina-

tion of solvatochromic shifts in the spectrum of acetone, done previously by our group[5], but now

using the CC2[6] method to obtain excitation energies and oscillator strengths; and (b) determina-

tion of the f -f spectrum of NpO2+2 using the Intermediate Hamiltonian Fock-space Coupled-Cluster

method[7], now having the actinyl ion embedded in Cs2UO2Cl4.

[1] T. A. Wesolowski and A. Warshel J. Phys. Chem. 97, 8050, 1993

[2] C. R. Jacob , J. Neugebauer, L. Jensen and L. Visscher PCCP, 8, 2349, 2006;

[3] P. Huang and E. A. Carter JCP, 125, 084102, 2006;

[4] (a) ADF: http://www.scm.com (b) Dalton: http://www.kjemi.uio.no/software/dalton/dalton.

html (c) Dirac: http://dirac.chem.sdu.dk

[5] J. Neugebauer, M. J. Louwerse, E. J. Baerends and T. A. Wesolowski JCP, 122, 094115, 2005

[6] H. Koch, O. Christiansen, P. Jorgensen and J. Olsen CPL, 244, 75, 1995

[7] I. Infante, A. Severo Pereira Gomes and L. Visscher JCP, 125, 074301, 2006

∗Electronic address: gomes@few.vu.nl†Electronic address: jacob@few.vu.nl‡Electronic address: visscher@chem.vu.nl

How Could AuF and XeAuF Be Synthesized in the Solid State?

Dominik Kurzydłowski1 and Wojciech Grochala1,2* 1 Faculty of Chemistry, The University of Warsaw, Pasteur 1, 02-093 Warsaw Poland;

2 ICM, The University of Warsaw, Pawińskiego 5a, 02-106 Warsaw Poland

The ‘simplest’ amongst fluorides of gold, AuF, has not been synthesized in bulk to this day; it has been characterized only in its molecular form in the gas phase, [1] and the search for a successful synthetic pathway towards AuF in the solid state is still on. [2] In this DFT (GGA/PBE) study we theoretically investigate various hypothetical polymorphs of AuF at ambient and at elevated pressures. [3] None of the four important structure types (NaCl, CsCl, AuCl and AuI) turns out to be a local minimum, since they exhibit imaginary phonons. Distortion of the parent structures along the normal mode of the img phonon, and subsequent geometry reoptimization, immediately brings a decrease in enthalpy for all structures. The new orthorhombic Cmcm polymorph (O1, see Figure) is a true minimum with the lowest enthalpy at 5 GPa among all structures studied; the Au–F stretching modes reach ~500 cm–1. Our calculations indicate, that the 1:2 mixture of AuF3 and elemental Au is likely to transform at 22.6 GPa into genuine metallic AuF, which in turn could subsequently be quenched to low pressures. [3] XeAuF, a hypothetical adduct of Xe to AuF (compare [2,4,5]), is another interesting story. We find that the quasi-molecular monoclinic P21/m structure (a derivative of the InOBr type) is the lowest enthalpy polymorph of XeAuF at 5 GPa. [6] AuI adopts a typical linear coordination with a short Au–Xe separation of 2.63 Å (see Figure) and the Au–F stretching mode at ~470 cm–1. At p > 15.8 GPa XeAuF outperforms the mixture of Xe, 1/3 AuF3 and 2/3 Au in enthalpy, but unfortunately the formation of XeAuF is prohibited by a side redox reaction (at p> 7.5 GPa) which leads to XeF2 and Au. [6]

Phonon dispersion curves and atomic contributions to the phonon DOS (left) for AuF in the new orthorhombic zig-zag chain structure at 5 GPa (center). The hypothetical XeAuF adduct in the

monoclinic dumbbell structure at 5 GPa (right).

Bibliography [1] K. L. Saenger and C. P. Sun, Phys. Rev. A 46 (1992) 670; P. Schwerdtfeger et al., Angew. Chem. Int. Ed. Engl., 33 (1994) 212; C. J. Evans and M. C. L. Gerry, J. Amer. Chem. Soc., 122 (2000) 1560; F. Mohr, Gold Bull., 37 (2004) 164. [2] S. Seidel and K. Seppelt, Science 290 (2000) 117. [3] D. Kurzydłowski and W. Grochala, Chem. Commun., submitted (2007). [4] P. Pyykkö, J. Am. Chem. Soc., 117 (1995) 2067; D. Schröder et al., Inorg. Chem., 37 (1998) 624. [5] W. Grochala, Chem. Soc. Rev. 36 (2007) 1632. [6] D. Kurzydłowski and W. Grochala, Z. Anorg. Allg. Chem., submitted (2007).

Simulation of LaCl3 in a water solution

D. Hagberg and L. Gagliardi

Department of Physical Chemistry

Sciences II University of Geneva, Switzerland

Late in the 19:th century it was discovered that electrolytes dissociated into their ions when

dissolved in an aqueous solution. It was later on discovered that the structure and the

number of water molecules around an ion is different for different ions. It is found that the

number of coordinating water molecules around an ion in the lanthanide series with a

charge 3+ should be between 8 and 9 [1]. X-ray diffraction studies was early used to study

the coordination number(CN) of the La3+ ion and showed that the average CN should be

around 9 [2].

In a recent study the hydrated ion concept was used to study the hydration of a Th(IV) ion

as an effect of different temperatures and chloride concentrations [3]. In our study we use a

full potential for all interacting species derived from quantum chemical calculations[4]. This

has been proven to be fruitful when charge transfer effects and many body induction energy

terms are accounted for [5,6]. The reason for this study is to see what kind of effect the ion

and counterion concentration has on the structure of the water molecules in the first and

second solvation shell around La3+. The idea is to do different simulations with different

concentrations of LaCl3 solvated in water to see how the concentration affects the structure

of the solvation shells.

In the current study an increased electrolyte concentration changes the coordination of

water molecules around the lanthanide ion. The calculations showed that a chloride ion tend

to exchanges a water molecule at the concentration of 0.5-1.0M LaCl3. The average

lanthanide water distance also starts do decrease when a chloride ion starts to substitute a

water molecule in the first solvation shell.

[1] Th. Kovall, F. Foglia, L. Helm and A. E. Merbach, JACS, 1995, 117, 3790

[2] A. Habenschuss and F. H. Spedding, J. Chem. Phys., 1979, 70, 3758

[3] T. Yang, S. Tsushima, A. Suzuki, Chem. Phys. Lett., 2002, 360, 534

[4] D. Hagberg, E. Bednarz, N. M. Edelstein, and L. Gagliardi, JACS, 2007, 129, 14136

[5] C. Clavaguéra, R. Pollet, J. M. Soudan, V. Brenner and J. P. Dognon, J. Phys. Chem A, 2005, 109, 7614

[6] D. Hagberg, G. Karlstrom, B. O. Roos, L. Gagliardi, JACS, 2005, 127, 14250

Relativistic two-component calculations of EPR parameters

for oxo-tungsten(V) and oxo-molybdenum(V) complexes

Peter Hrobárik, Olga L. Malkina, Vladimir G. Malkin

Institute of Inorganic Chemistry, Slovak Academy of Sciences, Bratislava, Slovakia.

A number of molybdenum and tungsten-containing enzymes play an important role in

biological two-electron redox processes. Due to the occurrence of paramagnetic MoV or WV

species during the catalytic cycles of all of these enzymes, EPR spectroscopy can be a

valuable tool to reveal details about the metal coordination sphere. However, it is often

difficult to interpret these EPR spectra or even to find a unique set of EPR parameters for

them. Thus, models or theories that are able to provide the link between molecular structure

and EPR parameters are needed.

In our recent papers [2-3], we have shown that Δg|| component in oxo-molybdenum(V)

complexes is insufficiently described by the usual second-order perturbation approach and

depends on higher-order spin-orbit contributions. Much more pronounced spin-orbit effects

are expected in analogous WV complexes. Therefore we decided to perform two-component

g-tensor calculations [1] based on the relativistic Douglas-Kroll-Hess Hamiltonian with

variational inclusion of spin-orbit coupling for several biologically relevant oxo-tungsten(V)

as well as oxo-molybdenum(V) model complexes. Unlike one-component perturbational

approach, the two-component scheme reproduces successfully large negative Δg|| values and

gives excellent accord with experiment. Scalar relativistic effects enhance the isotropic Mo

and W hyperfine coupling by about 15-30%. The effect of a finite-size nucleus model is also

discussed.

[1] Malkin, I.; Malkina, O. L.; Malkin, V. G.; Kaupp, M. J. Chem. Phys. 2005, 123, 244103.

[2] Fritscher, J.; Hrobárik, P.; Kaupp, M. J. Phys. Chem. B 2007, 111, 4616.

[3] Fritscher, J.; Hrobárik, P.; Kaupp, M. Inorg. Chem. 2007, 46, 8146.

[4] Hrobárik, P.; Malkina, O. L.; Malkin, V. G.; in preparation.

Computational Study of Bonding Trends in The Metalloactinyl Series

EThM and MThM’ (E = N-, O, F+; M, M’ = Ir-, Pt, Au+)

Peter Hrobárik 1,2, Michal Straka 2, Pekka Pyykkö 2

1 Institute of Inorganic Chemistry, Slovak Academy of Sciences, Bratislava, Slovakia. 2 Department of Chemistry, University of Helsinki, Finland.

A chemical analogy between oxygen and platinum (or Au+) was recently discovered for

multiply-bonded molecular systems, with the O/Pt at the end of chemical bond. Similar

analogies, such as N/Ir, hold for the neighbouring transition metals. This idea was applied to

replacing main-group atoms in uranyl UO22+ or isoelectronic systems by Gagliardi and

Pyykkö [1], who also found well-developed triple bonds at both ends, E≡U and U≡M(nd).

The first member of the predicted series, OUIr+, was already experimentally produced in the

gas-phase [2]. The related OUAu+ and OUPt+ as well as other triatomics were also mass-

spectroscopically observed. Furthermore, UIr+, UPt+ UAu+ and other diatomics were found

and large dissociation energies were reported for some of them. The isoelectronic thinking

mentioned above suggests an entire family of metalloactinyls, where one or both maingroup

elements are replaced by transition metals. It is interesting to see what changes, if any, would

occur when passing from the normal actinyls to metalloactinyls.

The title systems, including EThE’, were treated at DFT level using a B3LYP functional and

small-core quasirelativistic pseudopotentials. Most of the studied systems are bent, like their

isoelectronic ThO2 analogue, except for some anionic systems containing Ir. The bond lengths

vary considerably and can lie above or below the sum of triple-bond covalent radii.

Preliminary evidence is found for multiple bonding of order higher than three in certain cases.

These involve δ-type donation from the 5d element to the actinide, and also a bonding

combination of outer σ doughnut orbitals. Among the studied systems, the iridium containing

species show the strongest back-donation to Th.

[1] Gagliardi, L.; Pyykkö, P. Angew. Chem. Int. Ed. 2004, 243, 1573; and references cited therein.

[2] Santos, M.; Marcalo, J.; Pires de Matos, A.; Gibson, J. K.; Haire, R. Eur. J. Inorg. Chem. 2006,

3346.

[3] Hrobárik, P.; Straka, M.; Pyykkö, P. Chem. Phys. Lett. 2006, 431, 6.

Gd/Cm(III) sorption onto aluminum oxides/hydroxides

N. Huittinen1, Th. Rabung

2, J. Lützenkirchen

2, H. Geckeis

2, J. Lehto

1

1University of Helsinki, Laboratory of Radiochemistry, P.O. Box 55,

FIN-00014, University of Helsinki, Finland 2Institut für Nukleare Entsorgung, Forschungszentrum Karlsruhe,

Postfach 3640, D-76021 Karlsruhe, Germany

Different to the various Al2O3 phases, gibbsite (α-Al(OH)3) represents a thermodynamically

stable solid phase in aqueous solutions and does not form surface alteration products when

suspended in water. In order to complete previous studies on actinide sorption to γ-Al2O3, we

investigated the sorption of Gd/Cm(III) to a pure synthesized gibbsite.

The solid was prepared by precipitation of aluminum hydroxide and subsequent dialysis at

elevated temperature (70°C) for a time span of 4 months. The product was fully characterized by

XPS, AFM, XRD, BET, SEM, TG and DTA. The pH dependent metal ion sorption was studied

in batch sorption experiments at two different ionic strengths (0.1M NaClO4/NaCl and 0.01M

NaCl) using Gadolinium as a model for trivalent actinides. The Gd concentration was varied

between 4 orders of magnitude from 6.4*10-9 M to 6.4*10

-5 M at a constant gibbsite

concentration of 2 g/l. All experiments were conducted in a glove box under Ar atmosphere to

exclude the influence of atmospheric CO2. Phase separation was achieved by ultracentrifugation

at 18000 and 90000 rpm and the Gd concentration in the supernatant was determined with ICP-

MS. pH edges are congruent at Gd concentrations up to 6.4*10-7 M indicating ideal linear

sorption behaviour. By further increasing the metal ion concentration, the pH edges shift to

higher pH values, typical for the non-ideal sorption range. No significant influence of ionic

strength was observed.

TRLFS experiments with Curium clearly show the presence of inner-sphere surface complexes.

In the pH range 4 to 11.5 two different surface sorbed Cm species can be differentiated from their

TRLFS peak positions. An additional strongly red-shifted fluorescence peak appears at 609 nm

and is assigned to a species incorporated into the Al(OH)3 structure. Variation of the solution pH

from 4 to 7 results in oversaturation of dissolved Al species with regard to gibbsite and coverage

of the surface sorbed Cm by the newly formed solid. By increasing the pH further to > 11 reduces

the contribution of the incorporated Cm species in the TRLFS spectra presumably due to

increasing Al solubility in this pH range. The studies demonstrate the significant impact of pH

dependent dissolution and precipitation of the solid phase during sorption experiments on the

speciation of surface sorbed metal ions and sorption mechanisms.

DIRECT LASER EXCITATION-INDUCED NMR SPLITTING:A Case for Completeness-Optimized Basis Sets

Suvi Ikäläinen, Pekka Manninen, Perttu Lantto and Juha Vaara

Laboratory of Physical Chemistry, Department of Chemistry, P.O.B. 55,A.I. Virtasen aukio 1, FIN-00014 University of Helsinki, Finlandemail: suvi.ikalainen@helsinki.fi

Irradiation of matter with a circularly polarized laser (CPL) beam distorts the electroncloud and produces a current density. In what is known as the inverse Faraday effect,this current density leads to a magnetic interaction equivalent to a static magnetic field atthe nucleus [1]. As a result, splitting in the nuclear magnetic resonance (NMR) spectrallines will occur. It has been proposed that irradiation witha CPL beam might lead toenhancements in determining molecular structures from NMRspectra [1]. With typicallaser beams that can be used in NMR experiments, the expectedshifts obtained fromearlier research have been too small to be observable [2]. Itwas, however, observedin [2] that when approaching optical resonance, the splittings for atomic Ne, Kr and Xeincrease exponentially. It was also predicted that splittings would increase for systemswith increasing polarizability.

NMR splittings were calculated for hydrocarbon systems of increasing complexity andpolarizability using both correlatedab initio wave function theories and density-functionaltheory (DFT), on the Dalton program [3]. The examined systems are ethene (C2H4),benzene (C6H6), coronene (C24H12) and fullerene (C60). Due to the very high demandsplaced by this time-dependent third-order molecular property, reliable results cannot beobtained with traditional Gaussian basis sets. We used the novel concept of completeness-optimized basis sets [4] that were generated using the Kruununhaka program [5]. Thesebasis sets are compact sets of functions that are optimized to fully simulate (in the senseof having unit overlap with) an arbitrary Gaussian functionwith its exponent in a certainrange.

The splittings increase with system size, showing directionally resolved, massive reso-nances around optical excitation energies. Simultaneously, these resonances are loweredtowards technologically accessible laser frequencies. Comparison withab initio resultsindicates that this property provides a challenging test for the performance of the differentDFT functionals.

[1] A. D. Buckingham and L. C. Parlett, Science 264 (1994) 1748; Molecular Physics 91(1997) 805.

[2] R. H. Romero and J. Vaara, Chemical Physics Letters 400 (2004) 226.[3] Dalton, a Molecular Electronic Structure Program, Release 2.0 (2005).[4] P. Manninen and J. Vaara, Journal of Computational Chemistry 27 (2006) 434[5] http://www.chem.helsinki.fi/ manninen/kruununhaka

How many hydrogen atoms can a metal bind ?

Ivan Infante1, Laura Gagliardi1, Xuefeng Wang2 and Lester Andrews2

Presenting author: Ivan Infante

Hydrogen can be stored either in its elemental form, as a gas or liquid, or in a chemical form. An ideal chemical hydrogen storage material should have a low molar weight, be inexpensive, have rapid kinetics for absorbing and desorbing H2 and store large quantities of hydrogen reversibly [1]. In this perspective, metal-hydrides are of considerable interest because in principle they can meet these requirements. The challenge of finding suitable candidates poses also another more chemical question, but equivalently interesting: what is the largest number of hydrogen atoms that a metal can bind? Recent studies suggested, for example, that WH4(H2)4 is a stable species and twelve hydrogens attached to a central metal represents a new record[2,3]. In the present work we present the results of a systematic study of poly-hydrogen compounds of lanthanides and actinides[4,5]. Inspection of the infrared absorption frequencies and their isotopic shifts in matrix isolation experiments, and comparison with calculated density functional theory frequencies has allowed us the identification of the species present in the matrix. The reaction of laser-ablated metal atoms co-deposited with pure hydrogen at 4 K forms several species identified as MHy(H2)x [ y= 2,3,4; x = 1,..,6-8 ; M=Lanthanide/Actinide]. The average binding energy per dihydrogen ligand in the MHy(H2)x complex is about 4-6 kcal/mol along all the series computed at the DFT/BP86/TZVPP level of theory including ZPE correction. The largest predicted coordinated complex is UH4(H2)8 , in which twenty hydrogen atoms are bound to the metal center. This represents a new record for metal hydride chemistry.

[1] Chem. Rev., 106(10), 2007, 3899. Special thematic issue on hydrogen. [2] L. Gagliardi, P. Pyykkö, J. Am. Chem. Soc., 126, 2004, 15014[3] X. Wang, L. Andrews, I. Infante, L. Gagliardi, submitted to J. Am. Chem. Soc.[4] Raab, R.H. Lindh, X. Wang, L. Andrews and L. Gagliardi J. Phys. Chem. 111 2007, 6383[5] I. Infante, L. Gagliardi, X. Wang and L. Andrews, in preparation

1Department of Physical Chemistry, University of Geneva, 30 Quai Ernest Ansermet, CH-1211 Geneva, Switzerland2Department of Chemistry, University of Virginia, Charlottesville, Virginia 22904-4319, United States

At what size do gold cluster anions become 3D?

Mikael P. Johansson1, Filipp Furche2, Detlef Schooss3

1Lundbeck Foundation Centre for Theoretical Chemistry, Aarhus University

mikael.johansson@iki.fi

2Institut für Physikalische Chemie, Universität Karlsruhe

3Institut für Nanotechnologie, Forschungszentrum Karlsruhe

Small gold cluster anions are known for their unique two-dimensional

structures giving rise to properties very different from those of bulk gold.

Experiment and theory have been at odds with respect to the specific point of

the transition to 3D structures. By combining trapped ion electron diffraction

and state of the art electronic structure calculations, we reconcile the

experimental and theoretical approaches. We identify two crucial theoretical

prerequisites: accurate jellium surface energies have to be provided, and spin-

orbit effects included. PBEsol [1] and TPSS [2] are shown to be first-choice

functionals for the study of gold clusters, and can be expected to perform well

for other, related systems.

[1] J. P. Perdew, A. Ruzsinszky, G. I. Csonka, O. A. Vydrov, G. E. Scuseria, L. A.

Constantin, X. Zhou, K. Burke, arXiv cond-mat/0711.0156

[2] J. Tao, J. P. Perdew, V. N. Staroverov, G. E. Scuseria, Phys. Rev. Lett. 91 (2003) 146401.

[3] M.P. Johansson, F. Furche, A. Lechtken, D. Schooss, M.M. Kappes (submitted)

The Chemistry of the CuB Site in Cytochrome c Oxidase

VILLE R. I. KAILA1, MIKAEL P. JOHANSSON3, 

 DAGE SUNDHOLM2, LIISA LAAKKONEN1, MÅRTEN WIKSTRÖM1

1 Helsinki Bioenergetics Group, Programme of Structural Biology and Biophysics, Institute of Biotechnology, University of Helsinki, P.O. Box 65, FI­00014 Helsinki, Finland 

2 Department of Chemistry, University of Helsinki, P.O. Box 55, FI­00014 Helsinki, Finland3 Department of Chemistry, University of Aarhus, Aarhus, Denemark

Abstract

The spectroscopically invisible CuB  site of heme­copper oxidases has been studied with hybrid density 

functional calculations. The site comprises a copper atom ligated to three histidines residues (His­240, 

His­290, His­291), and a tyrosine residue (Tyr­244) covalently bound to one of the histidines (His­240). 

Our recent results suggest that this site might dictate proton transfer in cytochrome c oxidase. We have 

optimized the structure of a large realistic model system (~110 atoms) of the CuB site in several different 

redox and  ligand states   that  are proposed  to  be  intermediates  in  the catalytic  cycle.  The optimized 

structures are practically  identical with the available crystal structures, but we find some redox state 

dependent alterations in bond lengths between the copper and its ligands. We observe a thus far unnoticed 

internal electron transfer between the copper atom and the tyrosine, which seems to be coupled to the 

unique His­Tyr bond. Localization of the electron on either copper or tyrosine seems to be determined by 

the oxygenous ligand of Cu. 

Multiconfigurational Character of the Actinocenes. i: Thorocene, Protactinocene, and Uranocene

Andrew Kerridge and Nikolas Kaltsoyannis

Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, UK

We perform all-electron spin-orbit coupled CASPT2 calculations on the first three actinocenes, thorocene, protactinocene, and uranocene. We consider states of each symmetry species of the molecular point group in order to identify the spin-orbit coupled free (SOF) ground state, and numerically optimise the ring-metal separations at the SOF-CASPT2 level, finding excellent agreement with experiment where available. We consider the multiconfigurational nature of the ground and excited states of these systems at their ground state geometries, and in all cases find a single-configuration ground state. Whilst spin-orbit coupling (SOC) is unimportant for thorocene, the situation is very different in protactinocene and uranocene, with qualitatively different results found when SOC is included.

An exact two-component theory based on the Normalised Elimination of the Small Component applied to core ionizations.

R. Klooster, M. Filatov and R. Broer

Presenting author: R. Klooster

In the quantum-chemical treatment of systems with heavy elements it is important to incorporate relativistic effects via the Dirac equation. For virtually all chemical problems, we are only interested in the positive energy solutions of this equation. It is therefore desirable to transform the four-component Dirac equation to a two-component form, effectively eliminating the negative energy solutions. In a matrix formulation, this can be done by the Normalized Elimination of the Small Component (NESC) algorithm. The small component is eliminated by expressing it in terms of the large component times a transformation matrix. This matrix is energy-dependent and therefore needs to be calculated iteratively. Transformed overlap, kinetic energy and potential energy matrices can then be defined to be used in subsequent many-electron calculations. We haveimplemented the spin-free (one-component) form of NESC in the MOLCAS package.

We apply NESC to the calculation of X-ray Photoelectron Spectra (XPS) of uranium. These calculations present a challenge, since a good description of core-ionized states requires a high level treatment of correlation effects, i.e. using Configuration Interaction (CI). Spin-orbit effects are included a posteriori using Restricted Active Space State Interaction (RASSI).

Theoretical Chemistry, Zernike Institute for Advanced Materials, Rijksuniversiteit Groningen, Nijenborgh 4,9747 AG Groningen, The Netherlands

Parallelization of large-scale relativistic multi-reference CI and

multiconfigurational self-consistent-field programs with application to

actinide diatoms.

Stefan Knecht†, Hans Jørgen Aa. Jensen‡ and Timo Fleig†

†Institute of Theoretical and Computational Chemistry, HHU Dusseldorf, Germany

‡Department of Physics and Chemistry, University of Southern Denmark, Denmark

Multi-reference configuration interaction (MR-CI) methods are particulary suited for the investi-

gation of ground or excited states of molecules that may exhibit multi-configurational character.

An accurate theoretical treatment of heavy-element systems requires in addition to high-level

relativistic ab initio correlation methods large and extensive basis sets. Regarding these require-

ments, the size of a typical calculation quickly becomes so large that a serial code can hardly be

applied in an acceptable time frame. Thus, high-level MR-CI calculations even on comparatively

small systems demand for parallel computing. For this purpose, we have implemented parallel

versions of both the string-driven spin-orbit free GAS (Generalized Active Space)-CI [1] program

LUCITA [2] based on the LUCIA code [3] and the four-component double-group GAS-CI pro-

gram LUCIAREL [4, 5] that is embedded in a KR-MCSCF [6, 7] environment. Both programs

are available within a local version of the DIRAC program package [8]. Furthermore, the ongoing

work on a fully parallelized four-component KR-MCSCF module will be presented.

The investigation of the electronic structure of the early actinides is a very active field of re-

search [9, 10]. In our current study of the actinide diatoms Th2 and U2 we are focussing in

particular on the effect of a rigourus treatment of spin-orbit coupling since the ground state of

these as well as of other actinide dimers feature many open-shells. By taking advantage of the

new parallel codes [11, 12] we will shed further light on the bonding pattern in particular for U2

based on a highly sophisticated level both w.r.t. electron correlation and basis set expansion.

References

[1] T. Fleig, J. Olsen, and C. M. Marian. J. Chem.Phys., 114:4775, 2001.

[2] T. Fleig and L. Visscher. Chem. Phys., 311:113, 2005.

[3] J. Olsen, P. Jørgensen, and J. Simons. Chem.Phys. Lett., 169:463, 1990.

[4] T. Fleig, J. Olsen, and L. Visscher. J. Chem.Phys., 119:2963, 2003.

[5] T. Fleig, H. J. Aa. Jensen, J. Olsen, and L. Visscher. J. Chem.Phys., 124:104106, 2006.

[6] H. J. Aa. Jensen, K. G. Dyall, T. Saue, and K. Fægri. J. Chem.Phys., 104:4083, 1996.

[7] J. Thyssen, H. J. Aa. Jensen and T. Fleig, J. Chem. Phys., under revision.

[8] DIRAC, a relativistic ab initio electronic structure program, developer version.

[9] L. Gagliardi and B. O. Roos. Nature, 433:848, 2005.

[10] B. O. Roos, P.-A. Malmqvist, and L. Gagliardi. J. Am. Chem. Soc., 128:17000, 2005.

[11] S. Knecht, H. J. Aa. Jensen and T. Fleig, J. Chem. Phys., accepted for publication.

[12] S. Knecht, H. J. Aa. Jensen and T. Fleig. Manuscript in preparation.

Optical Properties of Silicon Nanoclusters

Olli Lehtonen and Dage Sundholm

Presenting author: Olli Lehtonen

Light emitting silicon nanoclusters have been studied extensively during last years. However, the actual mechanism responsible for the strong optical activity of the nanoclusters has remained unsolved. The molecular structures and electronic excitation spectra of silicon nanoclusters up to Si329H196 have been studied using time-dependent density functional theory.The computed excitation energies are often in good agreement with the experimental observations, but the oscillator strengths of the transitions are usually significantly smaller than reported in experiments. We also propose new class of silicon nanoclusters with silane modified surface, which have both energies and oscillator strengths in accordance with experiments, as possible candidates for strongly luminescent silicon nanoclusters.

Department of Chemistry, University of Helsinki, Finland

Computational Studies on Triplet State Dynamics in Peridinin-Chlorophyll-a-Protein

Ying-Chan Lin1, Zhi-QiangYou2, Chao-Ping Hsu2, and Dage Sundholm1

1Department of Chemistry, University of Helsinki, Finland;

2Institute of Chemistry, Academia Sinica, Taiwan Peridinin (Per) in Peridinin-Chlorophyll-a-Protein (PCP) not only has an exceptional Light-Harvest (LH) function, but it is also efficient in photoprotecting protein and chromophore from degradation by singlet oxygen which leads a subsequent damages of the LH apparatus.1,2 In this case, Per with its low-lying triplet states quench long-lived chlorophyll (Chl) triplets.3

3Chl-a* + Per → Chl-a+ 3Per (chlorophyll triplet quenching) The formation of Per triplet states in PCP has been experimentally investigated in great detail by Alexandre et al.4 In this work, we first computationally estimate the electronic coupling of two triplet states by applying the fragment spin difference method5, and then examine the nature of the triplet-triplet energy transfer in PCP. [1] J. A. Bautista, R. G. Hiller, F. P. Sharples, D. Gosztola, M. Wasielewski, H. A. Frank, J. Phys. Chem.

A. 103, 2267 (1999) [2] F. J. Kleima, M. Wendling, E. Hofmann, E.J. G. Peterman, R. van Grondelle, and H. van Amerongen,

Biochemistry 39, 5184 (2000) [3] A. Damjanovic, T. Ritz, K. Schulten, Biophys. J. 79, 8012 (2000) [4] M. T. A. Alexandre, D. C. Lührs, I. H. M. van Stokkum, R. Hiller, M.-L. Groot, J. T. M. Kennis, and R.

van Grondelle, and H. van Amerongen, Biochemistry 93, 2118 (2000) [5] Z.-Q. You, C.-P. Hsu, (manuscript in preparation)

Platinum oxyfluorides: a new family of highly oxidized transition metal complexes

Sergio Alberto Losilla Fernández, Pekka Pyykkö and Sebastian Riedel

Presenting author: Sergio Alberto Losilla Fernández

For the first transition metals of the fifth row, synthesis of terminal-oxo complexes (LxM=O) is often simple; this type of bonds can be even found in biological systems. However, this does not hold for the elements of groups 9, 10 and 11: Ir, Pt and Au.

Among terminal oxo-complexes, oxyfluorides form an interesting subgroup. The presence of both fluorine and oxygen leads to very oxidized species, usually in the highest oxidation state possible. These species could offer very powerful oxidating and fluorinating capabilities, and the presence of fluorine could also lead to some interesting new properties. In this work, the gas-phase stabilities of a wide variety of platinum oxides and oxyfluorides have been studied at different levels of theory, ranging from DFT to CCSD(T). A number of species that have not been reported are predicted to be thermodynamically stable, and some others are local minima that are expected to be observable in matrix isolation conditions.

Department of Chemistry, University of Helsinki, Finland

Fully relativistic calculations on the potential energy surfaces of the lowest 23 states of molecular chlorine

Luiz Guilherme M. de Macedo1 Wibe A. de Jong 2

Presenting author: Luiz Guilherme M. de Macedo

The electronic structure and spectroscopic properties of the ground state and the 22 lowest excitedstates of chlorine molecule were studied within a four component relativistic framework using the MOLFDIR program package. The potential energy curves of all possible 23 covalent states were calculated using relativistic complete open shell configuration interaction (COSCI) approach. In addition, four component multi-reference configuration interaction with singles and doubles excitations (MRCISD) calculations were performed in order to infer the effects due to dynamical correlation in vertical excitations. The calculated properties are in good agreement with the available experimental data.

1Laboratório de Simulação Computacional, Departamento de Química, Universidade Estadual Paulista (UNESP), Bauru, SP 17033-360, Brazil

2William R. Wiley Environmental Molecular Laboratory, Pacific Northwest National Laboratory, P.O. Box 999, Richland, Washington 99352 USA

Study of the solution/vapor interface of ionic, zwitterionic surfactant and ionic liquids using molecular dynamics simulations.

Babak Minofa1, Michal Petrov, L. Vrbka, Patrick Kölsch2, Pavel Jungwirth, Jan Picálek3 and J. Kolafa3

Presenting author: Babak Minofar

An aqueous ionic surfactant 1-dodecyl-4-dimethylaminopyridinium (DMP) bromide and the corresponding zwitterion 2-(4-dimethylaminopyridinio)-dodecanoate (DPN) were explored by means of molecular dynamics (MD) simulations. The molecular structure of the interfacial layer was investigated for the ionic and zwitterionic systems as a function of surfactant concentration, both in water and in salt (KF or KBr) solutions, by MD simulations in a slab geometry. The different behavior of ionic and surfactant zwitterionic and the effect of the added salt were analyzed at a molecular level. The results of MD simulations were compared to those of nonlinear optical spectroscopy measurements. Infrared visible sum frequency generation (IR-VIS SFG) was employed to study the DMP ionic surfactant in water and upon addition of simple salts.[1] For ionic liquid we performed a detailed molecular dynamics study of the interfacial structure ofaqueous solutions of 1-butyl-3-methylimidazolium tetrafluoroborate and 1-butyl-3-ethyl-imidazolium hexafluorophosphate in order to explain the anomalous dependence of the surface tension on concentration. Both nonpolarizable and polarizable force fields have been employed. The initial decrease of surface tension was confirmed for both systems, while the increase at higher bulk concentrations was observed only for the more hydrophilic tetrafluoroborate anion. Propensity of butyl chains toward vacuum, the preferably parallel orientation of imidazolium rings, and the local balance of cations and anions at the surface layer were observed in accordance with experiment. Most surface phenomena are more pronounced if polarizability is taken into account.[2]

[1] Petrov, M.; Minofar, B.;; Vrbka, L.; Jugwirth, P.; Koelsch, P.; Motschmann, H.: Aqueous ionic and complementary zwitterionic soluble surfactants: Molecular dynamics simulations and sum frequency generation spectroscopy of the surfaces. Langmuir, 22 (2006) 2498.[2] Picalek, J.; Minofar, B.; Kolafa, J.; Jungwirth, P.: Aqueous solutions of ionic liquids: Study of the solution/vapor interface using molecular dynamics simulations. Journal of Chemical Physics C, submitted

1University of South Bohemia,Institute of Physical Biology, Zámek 136, 373 33 Nové Hrady,Czech Republic Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech, Flemingovo nám. 2, 16610 Prague 6, Czech Republic

2Max-Planck Institute of Colloids and Interfaces, Am Mühlenberg 2, 14476 Golm, Germany

3Department of Physical Chemistry, Institute of Chemical Technology, Prague; Technická 5, 16628 Praha 6, Czech Republic.

Ionic liquids at the Air/Water interface

Babak Minofar1,Jan Picálek2, J. Kolafa2,Pavel Jungwirth1

Presenting author: Babak Minofar

We performed a detailed molecular dynamics study of the interfacial structure of aqueous solutions of 1-butyl-3-methylimidazolium tetrafluoroborate and 1-butyl-3-methylimidazolium hexafluoro-phosphate in order to explain the anomalous dependence of the surface tension on concentration. Both nonpolarizable and polarizable force fields have been employed. The initial decrease of surface tension was confirmed for both systems, while the increase at higher bulk concentrations was observed only for the more hydrophilic tetrafluoroborate anion. Propensity of butyl chains toward vacuum, the preferably parallel orientation of imidazolium rings, and the local balance of cations and anions at the surface layer were observed in accordance with experiment. Most surface phenomena are more pronounced if polarizability is taken into account.

1Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic: Flemingovo nám. 2, 16610 Prague 6, Czech Republic.

2Department of Physical Chemistry, Institute of Chemical Technology, Prague; Technická 5, 16628 Praha 6, Czech Republic

Relativistic Energy-consistent 5f-in-core Pseudopotentials for Penta- and Hexavalent Actinides

A. Moritz and M. Dolg

Presenting author: A. Moritz

Analogous to the surprisingly well working 5f-in-core pseudopotentials corresponding to di-, tri-, and tetravalent actinides, relativistic energy-consistent 5f-in-core pseudopotentials corresponding topentavalent (5fn-2 occupation with n=2−6 for Pa−Am) and hexavalent (5fn-3 occupation with n=3−6 for U−Am) actinides have been adjusted. Results of Hartree-Fock test calculations for actinide penta- and hexafluorides are compared to corresponding calculations using 5f-in-valence pseudopotentials. While in the pentavalent case the 5f-in-core approximation is still quite accurate, its limitations seem to be reached in the hexavalent case.

Institute for Theoretical Chemistry, University of Cologne, Greinstr. 4, D-50939 Köln, Germany

Accurate Ground State Calculations of Diatomic Molecules Using Complete Orthonormal Basis

Sets of Exponential-Type Orbitals by Single-Zeta Approximation

Nergiz Ozcan and Ali Bagci

Presenting author: Nergiz Ozcan

The ground states energies of the diatomic molecules are calculated by employing complete orthonormal sets of Ψα-exponential type orbitals (Ψα-ETO) with the same orbital parameter zeta, for α=1,0,-1. Molecular orbitals linear combinations of atomic orbitals (MO-LCAO) method is used to determine the ground state energies of homonuclear (H2, He2, Li2) and heteronuclear (HeH+, LiH) molecules by employing the same screening constant for a given set of atomic orbitals of each molecular function. For each molecule, the calculations are carried out for values of nuclear separations 0.5 ≤ R ≤ 20, and Ψα-ETOs basis sets with α=1,0,-1. The results are in good agreement with those found in the literature.

An ab initio study of the photoinduced proton transfert on the uranyl in aqueous solution :

a first step towards the understanding of the yl-exchange reaction

F. Réal1, V. Vallet2, U. Wahlgren1 and I. Grenthe3 1 AlbaNova University Center, Stockholm University, Fysikum,

104-91 Stockholm, Sweden 2Laboratoire PhLAM, Université des Sciences et Technologies de Lille 1

CNRS UMR8523, 59655 Villeneuve d’Ascq Cedex, France 3KTH Royal Institute of Technology, Inorganic Chemistry

Se-100-44 Stockholm, Sweden.

The isotope exchange reaction U17O2

2+ + H2O UO22+ + H2

17O (1) is extremely slow under normal conditions and at low pH. The rate at high pH1 is significantly faster. This is also the case at low pH in the presence of uranyl(V)2. If the sample is irradiated by UV light the reaction rate increases dramatically3; this is in fact the standard method for enrichment of 17O in the uranyl(VI) ion4. However, neither the reaction mechanism nor the excited states involved in this photochemical process are known. The reaction proceeds in water but is inhibited if the equatorial water molecules are exchanged with other ligands5, which might indicate that the most likely reaction pathway involves a hydrogen transfer from coordinated water in the equatorial plane, followed by a geometrical re-arrangement. In addition, no exchange is observed for low excitation energy (daylight) and this suggests that the reaction involves higher excited states of uranyl(VI). In this work we have used quantum chemical methods to explore one possible reaction path for the oxygen-exchange in the uranyl(VI) penta aqua ion: it involves in the first step proton abstraction of the “yl”-oxygens, either from one coordinated water molecule, or from an outer-sphere water. We have followed this reaction profile in the ground state, in the luminescent state 3Δg (σu

1f1δ) and in a higher

lying excited state 3Γg, which corresponds to the excitation from the highest occupied πu orbitals to the fδ orbital. The calculations were performed without spin-orbit coupling using the time-dependant density functional theory method (TD-DFT). The computational results indicate that the 3Γg state, corresponding to an excitation from the π to the fφ, is a likely candidate for the photochemically “active” state where the increase of the U-Oyl distance localizes the wave function and gives the “yl” oxygen a radical character

1 H. Moll, T. Reich, A. Rossberg, Z. Szabó and I. Grenthe, Radiochim. Acta, 88, 559 (2000). 2 G. Gordon and H. Tauben, J. Inorg. Chem, 16, 189 (1961); G. Gordon and H. Tauben, J. Inorg. Chem, 16, 272 (1961); 3 a) C.P. Baird and T.K. Kemp, Prog Reaction Kinetics, 22,87 (1997). b) Z. Fazekas, H. Tomiyasu, Y.-Y Patk, T. Yamamura and M. Harade, ACH-models in Chemistry, 135, 735. c) A.B. Yusov, V.P. Shilov, Russ. Chem. Bull. Int. Ed, 49, 2000 (1925). d) S.J. Formosinho, H.F . Burrows, M. da Graça Miguel, M. E. D. G Azenha, I.M Saraiva, C. D. N. Ribeiro, I.V. Khudyakov, R.G Gasanov, M. Bolte and M. Sarakha, Photochem. Photobiol. Sci, 2, 569 (2003). 4 H.W. Crandall, J. Phys. Chem, 17, 602 (1949). 5 S. Szabó, V. Valler and I. Grenthe, manuscripts

Theoretical study of High and Low spin states of divalent lanthanides: Yb2+-doped CsCaBr3

Goar Sánchez, Luis Seijo, and Zoila Barandiarán

Presenting author: Goar Sánchez

It is nowadays possible to calculate the electronic structure of excited states of f-element ions doped in ionic crystals from first principles, using wavefunction based methods of relativistic quantum chemistry. No experimental data are required as input for the calculations whose outcome allows to discuss the local distortions, bonding properties, and spectroscopy (fn ↔ fn and fn ↔ fn-1d1), including band shapes and emission lifetimes of dipole allowed transitions, independently of the fact that the material has or has not been previously grown and experimentally studied. Work has been done in our group over the past few years on divalent and trivalent lanthanides, and trivalent and tetravalent actinides in halide hosts, which has served to check the accuracy and show the adequacy of the methods to help to interpret and to predict spectroscopic features, and work is in now in progress on the following lines: (i) Microscopic characterization of the excited states responsible for anomalous emission of Eu2+ in fluorite-like hosts (ii) Electronic structure of high- and low-spin states of divalent lanthanides (iii) Luminescence studies on materials for solid state lighting, such as Ce3+ -doped and co-doped YAG, and (iv) Local structure and spectroscopy of solid UO2. In this poster we will present the most recent results available on line (ii) for Yb2+-doped CsCaBr3. The work is being done in collaboration with experimental groups (Claudia Wickleder, University of Siegen).

Departamento de Química, C-XIV, Universidad Autónoma de Madrid and Instituto Universitario de Ciencia de Materiales Nicolás Cabrera, Universidad Autónoma de Madrid, 28049 Madrid, Spain.

Dynamics of nuclear motion in cyanoacetylene molecule and its complexes

with helium by state-of-the-art quantum mechanical methods.

Leonid Shirkov and Robert Moszyński

Quantum Chemistry Laboratory, Faculty of Chemistry, University of Warsaw, ul. L. Pasteura 1, 02-093 Warszawa, Poland

Abstract

Theoretical description and computational modeling of the spectroscopic and collisional

processes involving cyanoacetylene HC3N in the interstellar environment is our main

scientific object. Modeling of the interstellar medium requires the knowledge of the rate

constants for rovibrational (de)excitation of molecules with the most abundant species such as

helium.

Theoretical study of the spectroscopy of the cyanoacetylene molecule is based on the

Watson’s isomorphic Hamiltonian describing the rovibrational motions in linear polyatomic

molecules, including the anharmonicity effects to infinite order, as well as the Corriolis

coupling of the total angular momentum of the molecule with the vibration angular momenta

corresponding to degenerate vibrational modes. The potential energy surface for the

intramolecular dynamics is computed with the state-of-the-art methods of quantum chemistry.

The eigenvalues of the Hamiltonian matrix were computed using the modified Davidson

algorithm for large, sparse, real-symmetric matrices and plausible results were obtained.

As the next step, we consider of the rovibrational (de)excitation of HC3N in collisions

with He. A Hamiltonian describing the nuclear motions in the collisional complexes was

already derived, including the coupling of the vibrational angular momentum of the molecule

with the total angular momentum of the collisional complex. Potential energy surface for He-

HC3N generated by symmetry-adapted perturbation theory including its dependence of the

intramolecular degrees of freedom and, finally, with the new scattering codes treating the

rovibrational dynamics of He-HC3N the rate constants for the rovibrational (de)excitation will

be written. Applications of the computed potential surface to high-resolution spectroscopy of

the He-HC3N are also considered. References [1] James K.G. Watson Mol. Phys., 1968, Vol. 15, No. 5, 479-490 [2] James K.G. Watson Mol. Phys., 1970, Vol. 19, No. 4, 465-48 [3] B.J. Howard and R.E. Moss, Mol. Phys., 1971, Vol. 20, No. 1, 147-159 [4] P. Botschwina, Mol. Phys., Vol. 103, No. 10, 20, 05/2005 [5] R. Bukowski, K.Szalewicz, J. of Ch. Ph., Vol. 119, N.16, 10/2003

Implementation and Initial Application of Multi-Reference

Coupled-Cluster

Lasse Kragh Sørensen, Timo FleigDepartment of Theoretical Chemistry, Heinrich Heine University Dusseldorf,Universitatsstraße 1, D-40225 Dusseldorf, Germany

Jeppe OlsenDepartment of Chemistry, University of Aarhus, Langelandsgade 140, DK-8000Aarhus C, Denmark

We present the initial implementation of a determinant-based general-order coupled cluster [1] method which fully accounts for relativistic effectswithin the four-component framework [2]. The method opens the way for thetreatment of multi-reference problems through a state-selective expansion ofthe model space. The evaluation of the coupled cluster vector function is car-ried out via relativistic configuration interaction expansions. Current workis focussed on a commutator-driven evaluation of the CC vector function.

We demonstrate the capabilities of the new method in calculations ofcomplete potential energy curves of the HBr[3] molecule. The inclusion ofspin-orbit interaction and higher excitations than coupled cluster double ex-citations, either by multi-reference model spaces or the inclusion of full iter-ative triple excitations, lead to highly accurate results for spectral constantsof HBr.

[1] J Olsen, The initial implementation and applications of a general active spacecoupled cluster method, jcp, 2000, 113, 7140[2] “dirac04, a relativistic ab initio electronic structure program, Release dirac04.0(2004)” , Written by H. J. Aa. Jensen and T. Saue and L. Visscher with contribu-tions from V. Bakken and E. Eliav and T. Enevoldsen and T. Fleig and O. Fos-sgaard and T. Helgaker and J. Laerdahl and C. V. Larsen and P. Norman andJ. Olsen and M. Pernpointner and J. K. Pedersen and K. Ruud and P. Salek andJ. N. P. van Stralen and J. Thyssen and O. Visser and and T. Winther., 2004[3] Timo Fleig, Lasse K. Srensen, and Jeppe Olsen, A Relativistic 4-ComponentGeneral-Order Multi-Reference Coupled-Cluster Method. Initial Implementationand Application to HBr, Theo Chem Acc (2007), DOI: 10.1007/s00214-007-0265-y

On the stability of Th-Th triple bonding

Michal Straka, Sebastian Riedel

Presenting author: Michal Straka, Sebastian Riedel

In our recent study (JACS 127,2005,13090) the theoretical evidence for linear HThThH with a triple Th−Th bond was presented. In this work we study analogous XThThX (X=F, Cl, Au, CN, CCH, CH3, SiF3, CF3, Cp-,C5F5) systems and discuss the stability of the triple bond with respect to ThX4, Th2X4 and Th2X6.

Department of Chemistry, University of Helsinki, Finland

Calculation of magnetically induced currentdensities in nano-sized systems

Dage Sundholm1, Jonas Juselius2 and Jurgen Gauss3

1 Department of Chemistry, University of Helsinki, Finland2 Department of Chemistry, University of Tromsø, Norway2 Institut fur Physikalische Chemie, Universitat Mainz, Germany

A method for calculating the magnetically induced current and spin densities using

gauge-including atomic orbitals (GIAO) is described [1,2]. The method is formulated in the

framework of analytical derivative theory. It has been implemented at the Hartree-Fock

self-consistent-field (HF-SCF), density functional theory (DFT), and ab initio coupled-

cluster levels. The gauge including magnetically induced current (GIMIC) method has

been applied in studies on nanosized molecules at the DFT level [3]. Quantitative values

for the induced currents passing molecular bonds are obtained by numerical integration

of the current flow. The obtained current susceptibilities can be used as a measure of the

electron delocalization or molecular aromaticity. The method has been used in studies of

magnetically induced current pathways for molecules consisting of connected rings such as

porphyrins, hexabenzocoronene [1], and fullerenes [3]. Recent applications of the method

to nano-sized systems will be presented.

[1] J. Juselius, J. Gauss, D. Sundholm, J. Chem. Phys. 121 (2004) 3952.

[2] Juselius, J. Gauss, D. Sundholm, manuscript.

[3] M.P. Johansson, J. Juselius, D. Sundholm, Angew. Chem. Int. Ed. 44 (2005) 1843.

Email: sundholm@chem.helsinki.fi

MAGNETIC PROPERTIES AND INTERNAL DYNAMICS OF Sc !C"@C#$%

S % Taubert & M % Straka & T % O % Pennanen & D % Sundholm & and J % Vaara

Department of Chemistry! P"O" Box ## $A" I" Virtasen aukio %&! FIN'(((%) University of

Helsinki! Finland"

Recent '!C nuclear magnetic resonance experiments (NMR) and crystal X*ray*experiments show

that the endohedral scandium fullerene Sc!C#" is in fact Sc!C"@C#$ +'& ",% By quantum chemical

calculations two stable isomers& close to each other in energy& were found +!,% We have

investigated this molecule by means of density*functional theory (DFT) calculations using the

GGA functional BP#- and basis sets of triple*zeta quality +.,% We have calculated the '!C NMR

chemical shifts for the closed*shell anion and the paramagnetic '!C NMR chemical shifts for the

open*shell neutral forms of Sc!C"@C#$% In both cases the endohedral carbons have a dramatically

larger chemical shift than the cage carbons& not seen in experiment% The paramagnetic chemical

shift is very different for the cage carbons in the two different isomers and this suggests it could

experimentally provide insight about the preferred conformation of this molecule% The A* and g*

tensors have also been calculated and are seen to depend strongly on the conformer% In order to

understand the dynamics of Sc!C"@C#$& we have performed first principles molecular dynamics

simulations at both high (/$$ K) and low ('/$ K) temperature% The dynamics of the scandium

atoms is more strongly coupled to the cage but than to the endohedral carbons& which also move

faster% Substantial internal motion takes place already at a picosecond time scale and both NMR

and EPR properties are expected to be averaged%

References

'% Y% Iiduka& T% Wakahara& T% Nakahodo& T% Tsuchiya& A% Sakaruba& Y% Maeda& T% Akasaka& K% Yoza&

E% Horn& T% Kato& M% T% H% Liu& N% Mizorogi& K% Kobayashi and& S% Nagase& J" Am" Chem" Soc" '"0

("$$/) '"/$$*'"/$'%

"% E% Nishibori& I% Terauchi& M% Sakata& M% Takata& Y% Ito& T% Sugai& and H% Shinohara& J" phys" Chem"

B ''$ ("$$-) '1"'/*'1"'1%

!% K% Tan and X% Lu& J" Phys" Chem% ''$ ("$$-) ''0'*''0-%

.% S% Taubert& M% Straka& T% O% Pennanen& D% Sundholm& and J% Vaara& Manuscript under

preparation%

A London-Like Formula For Endohedral Dispersion Interactions

Pekka Pyykkö, Cong Wang, Michal Straka, and Juha Vaara

Presenting author: Cong Wang

A London-type formula is derived for endohedral systems. It involves the static dipole polarisability, α1(A) of the inner system, A, and a new type of dipole polarisability, α-2(B) with an r-2 radial operator, for the outer system, B. The new formula has no explicit dependence on the radius, R, of B. The predicted interaction energies are compared against MP2 supermolecular calculations for A@C60, A = He-Xe, Zn, Cd, Hg, and CH4.

Department of Chemistry, University of Helsinki

An investigation of the accuracy of DFT functionals and choice of solvent model for the studyof the coordination of actinide species.

Pernilla Wåhlin1, Valérie Vallet3, Cécile Danilo1,3, Florent Réal3, Jean-Pierre Flament3 and Ulf Wahlgren1,2

Presenting author: Pernilla Wåhlin

In our ongoing study of the water exchange mechanism for the photo-excited uranyl(VI) aqua ion we found a need of a more thorough investigation of the accuracy of density functional theory (DFT) when applied on actinide complexes by comparing its performance to wave-function based correlated methods. Another question is the choice of solvation model and the number of coordinated water molecules which need to be included explicitly. There are a number of investigations on the water exchange mechanism for the uranyl(VI) aqua ion in its electronic ground state with different models.

In the investigation of the DFT accuracy, we used the water-exchange reactions in the uranyl(VI) aqua ion which takes place both in the electronic ground state and the first excited state (the luminescent 3Δg state) [1]. The geometries of the reactant and intermediates were optimized using the B3LYP functional, with a restricted closed-shell formalism for the electronic ground state and either an unrestricted open-shell formalism or the time-dependant (TD-) DFT method for the 3?g state. The relative energies have been computed with wave-function based methods, Møller-Plesset second-order perturbation theory (MP2), or a minimal multi-reference perturbative calculation (minimal CASPT2), coupled-cluster method (CCSD), and DFT with the hybrid functionals B3LYP and BHLYP and a number of pure correlation and exchange functionals, and the hybrid DFT-MRCI method. The results obtained with MP2 are in excellent agreement with those obtained with the CCSD method. However, DFT methods overestimate the energies in the case of high coordination numbers, yielding too high and too low reaction energies for the associative and dissociative reactions, respectively. Part of the errors appear to be associated with the amount of Hartree-Fock exchange used in the functional; for the dissociative intermediate in the ground state the pure DFT functionals underestimate the reaction energy by 20 kJ/mol.

In the model investigation, we have compared the uranyl(VI) aqua ion (ground state) with a total of 18 water molecules in the first and second coordination spheres with small models with a total of 6 water molecules. In the latter the water in the second coordination sphere is hydrogen bonded either to one or two of the water in the first sphere. The reactant and intermediates were again optimized using the B3LYP functional. The result so far, indicates that the energy difference in reaction energy between different models arises from the change in bond distance between uranyl and first coordination sphere but also the U-Oyl distance.

[1]P. Wåhlin, C. Danilo, V. Vallet, F. Réal, J.-P. Flament, U. Wahlgren, submitted to J. Chem. Theory.Comput.

1Department of Physics, Stockholm University, AlbaNova University Centre, 106 91 Stockholm, Sweden2NORDITA, AlbaNova University Centre, 106 91 Stockholm, Sweden3Laboratoire PhLAM, Université des Sciences et Technologies de Lille 1, CNRS UMR8523, 59655 Villeneuve d'Ascq Cedex, France

List Of Participants

Mr Huseyin AksuCanakkale,Turkey-

Prof Lester AndrewsCharlottesville, USAlsa@virginia.edu

Dr Markus Klaus ArmbrusterEggenstein-Leopoldshafen, Germanymarkus.armbruster@ine.fzk.de

Dr Michiko AtsumiHelsinki, Finlandatsumi@chem.helsinki.fi

Dr Ali BagciCanakkale, Turkeyali.bagci@yahoo.com.tr

Dr Zoila BarandiaranMadrid, Spainzoila.barandiaran@uam.es

Dr Noemi BarrosMadrid, Spainnoemi.barros@uam.es

Mr Reda BelmecheriVilleneuve d'Ascq Cedex, Francereda.belmecheri@phlam.univ-lille1.fr

Ms S. Maya BeyhanAmsterdam, The Netherlandsmbeyhan@few.vu.nl

Mr Lukas BucinskyBratislava, Slovakialukas.bucinsky@stuba.sk

Mr Kolawole Adetomiwa BusariUppsala, Swedenkollyb@gmail.com

Dr Steve ConradsonLos Alamos, USAconradson@lanl.gov

Prof Kit CumminsMassachusetts, USAccummins@mit.edu

Ms Cecile DaniloVilleneuve d'Ascq Cedex, Francececile.danilo@phlam.univ-lille1.fr

Mr Lukas DemovicBratislava, Slovakialukas.demovic@gmail.com

Dr Jean-Pierre DognonGif Sur Yvette Cedex, Francejean-pierre.dognon@cea.fr

Prof Michael DolgCologne, Germanym.dolg@uni-koeln.de

Dr Fatemeh ElmiHelsinki, Finlandfatemeh@chem.helsinki.fi

Mr Ndimiyang WilsonFondom, Cameroon -

Dr John GibsonBerkeley, USAjkgibson@lbl.gov

Prof Ingmar GrentheStockholm, Swedeningmarg@kth.se

Dr Wojciech GrochalaWarsaw, Polandwg22@cornell.edu

Dr Daniel HagbergGeneva, Switzerlanddaniel.hagberg@chiphy.unige.ch

Prof Lauri HalonenHelsinki, Finlandlauri.halonen@helsinki.fi

Ms Laureline HormaineStrasbourg, Francearesielle@aol.com

Mr Peter HrobarikBratislava, Slovakiapeter.hrobarik@savba.sk

Ms Nina HuittinenHelsinki, Finlandnina.huittinen@helsinki.fi

Ms Suvi IkäläinenHelsinki, Finlandsuvi.ikalainen@helsinki.fi

Dr Ivan InfanteGeneva, Switzerlandiinfant76@gmail.com

Dr Mikael JohanssonAarhus, Denmarkmikael.johansson@iki.fi

Mr Ville KailaHelsinki, Finlandville.kaila@helsinki.fi

Prof Nik KaltsoyannisLondon, United Kingdomn.kaltsoyannis@ucl.ac.uk

Dr Antti KarttunenJoensuu, Finlandantti.karttunen@joensuu.fi

Ms Joanna KauczorAarhus, Denmarkjoanna@chem.au.dk

Dr Andrew KerridgeLondon, United Kingdoma.kerridge@ucl.ac.uk

Mr Rob KloosterGroningen, The NetherlandsR.Klooster@rug.nl

Mr Stefan KnechtDuesseldorf, Germanystefan@theochem.uni-duesseldorf.de

Dr Henrik KonschinHelsinki, Finlandkonschin@chem.helsinki.fi

Prof Jouko Korppi-TommolaJyväskylä, Finlandktommola@jyu.fi

Mr Dominik KurzydłowskiWarsaw, Polandd.kurzydlowski@student.uw.edu.pl

Prof Jukka Lehto Helsinki, Finlandjukka.lehto@helsinki.fi

Dr Olli LehtonenHelsinki, Finlandolehtone@chem.helsinki.fi

Ms Ying-Chan LinHelsinki, Finlandyingchan@chem.helsinki.fi

Dr Mikko LinnolahtiJoensuu, FinlandMikko.Linnolahti@joensuu.fi

Mr Sergio Alberto Losilla FernándezHelsinki, Finlandsergio@chem.helsinki.fi

Dr Jan LundellHelsinki, Finlandjan.lundell@helsinki.fi

Dr Luiz MacedoHelsinki, Finlandluiz@chem.helsinki.fi

Dr Pekka ManninenEspoo, Finlandpekka.manninen@csc.fi

Dr Babak MinofarNove Hrady, Czech Republicminofar@greentech.cz

Dr Hirotoshi MoriAmes, USAhiro@si.msg.chem.iastate.edu

Ms Anna MoritzCologne, Germanyamoritz@uni-koeln.de

Dr Belen OrdejonTarragona, Spainbelen.ordejon@gmail.com

Mrs Nergiz OzcanHelsinki, Finlandnergizozcan@comu.edu.tr

Dr Petra J. PanakKarlsruhe, Germanypanak@ine.fzk.de

Dr Michael PatzschkeHelsinki, Finlandmichaelp@chem.helsinki.fi

Mrs Miia PehkonenHelsinki, Finlandmiia.pehkonen@helsinki.fi

Mr Teemu O. PennanenHelsinki, Finlandteemu.pennanen@helsinki.fi

Prof Russel PitzerColumbus, USApitzer@chemistry.ohio-state.edu

Prof Pekka PyykköHelsinki, FinlandPekka.Pyykko@helsinki.fi

Dr Florent RealVilleneuve d'Ascq Lille, Francereal@phlam.univ-lille1.fr

Dr Qinghua RenHelsinki, FinlandQinghua.Ren@helsinki.fi

Mr Michal RepiskyBratislava, Slovakiamichal.repisky@savba.sk

Dr Sebastian RiedelHelsinki, Finlandsriedel@psichem.de

Prof Björn RoosLund, Swedenbjorn.roos@teokem.lu.se

Dr Nino RunebergEspoo, Finlandruneberg@csc.fi

Dr Ilya RyabinkinMoscow, Russian Federationilya@phys016-amd3.chem.msu.ru

Prof Markku RäsänenHelsinki, Finlandmarkku.rasanen@helsinki.fi

Prof Notker RöschMunich, Germanyroesch@theochem.tu-muenchen.de

Mr Goar SanchezMadrid, Spaingoar.sanchez@uam.es

Mr Thomas Olof SandbergÅbo, Finlandtsandber@abo.fi

Dr Bernd SchimmelpfennigKarlsruhe, GermanyBernd.Schimmelpfennig@ine.fzk.de

Mr Moritz SchmidtKarlsruhe, Germanymoritz.schmidt@ine.fzk.de

Mr George SchoendorffAmes, USAgschoend@iastate.edu

Dr Andre Severo Pereira GomesAmsterdam, The Netherlandsgomes@few.vu.nl

Prof Shantanu SharmaPomona, USAsks@csupomona.edu

Mr Leonid ShirkovWarsaw, Polandleonid.shirkov@tiger.chem.uw.edu.pl

Mr Stanislav StandaraHelsinki, Finlandstanislav.standara@helsinki.fi

Dr Michal StrakaHelsinki, Finlandstraka@chem.helsinki.fi

Dr Dage SundholmHelsinki, Finlandsundholm@chem.helsinki.fi

Dr Tom SundiusHelsinki, FinlandTom.Sundius@helsinki.fi

Mr Lasse Kragh SørensenDuesseldorf, Germanylasse@theochem.uni-duesseldorf.de

Mr Jukka Tapani TanskanenJoensuu, Finlandjukka.tanskanen@joensuu.fi

Mr Matthew John TassellLondon, United Kingdommtassell@gmail.com

Mr Stefan TaubertHelsinki, Finlandstefan.taubert@helsinki.fi

Mr Erik TellgrenOslo, Norwayerik.tellgren@kjemi.uio.no

Mr Thuat TrinhEindhoven, The Netherlandst.t.trinh@tue.nl

Mr Sascha TrummKarlsruhe, Germanysascha.trumm@ine.fzk.de

Dr Juha VaaraHelsinki, Finlandjuha.t.vaara@helsinki.fi

Dr Valérie ValetLille, Francevalerie.vallet@univ-lille1.fr

Mr Cong WangHelsinki, Finlandeclipse@chem.helsinki.fi

Mr Ville WeijoEspoo, Finlandville.weijo@helsinki.fi

Prof Luuk VisscherAmsterdam, The Netherlandsvisscher@chem.vu.nl

Mr Tommy VänskäHelsinki, Finlandtommy@chem.helsinki.fi

Ms Pernilla WåhlinStockholm, Swedenpernilla@physto.se

Mr Patryk Zaleski-EjgierdHelsinki, Finlandteopze@chem.helsinki.fi

Mr Marcin ZiółkowskiAarhus, Denmarkmarcin@chem.au.dk

Mr N. SanthanamoorthiCoimbaotre, Indiasanthanamoorthi@yahoo.co.in