Theoretical Chemistry: Molecular Spectroscopy and Dynamics

THEORETICAL CHEMISTRY: MOLECULAR SPECTROSCOPY AND DYNAMICS 263CHIMIA 2004, 58, No. 5

Chimia 58 (2004) 263–275© Schweizerische Chemische Gesellschaft

ISSN 0009–4293

EDITORIAL AND REVIEW

Theoretical Chemistry: Molecular Spectroscopy and Dynamics39th Symposium on Theoretical Chemistry 2003 (STC 2003)28 September to 2 October 2003, Gwatt, Lake Thun, Switzerland#

Fabio Mariottia, Martin Quacka*, Martin Willekea, and Jürgen Stohnerb

Abstract: We provide a short review of the scientific meeting defined by the title of this article, which may at thesame time serve as a compact review of the field with a substantial number of references to recent work. Excitingnew developments in experiments on high-resolution molecular spectra and their analysis as well as new theoret-ical developments in the calculations of such spectra and the related time-independent and time-dependent quan-tum dynamics of molecules have led to new answers but also to new questions in the fields of molecular kinetics,molecular reaction dynamics, molecular chaos and statistical mechanics as well as fundamental symmetries in mo-lecular processes. Particular stress is placed on fundamental aspects and new directions.

Keywords: Chemical reaction kinetics · Molecular dynamics · Molecular spectroscopy · Quantum chemistry ·Theoretical chemistry

*Correspondence: Prof. M. QuackaPhysical ChemistryETH Zürich (Hönggerberg)CH-8093 ZürichTel.: +41 1 632 44 21Fax: +41 1 632 10 21E-Mail: [email protected]://www.ir.ethz.ch/ bInst. of Chemistry and Biological ChemistryZHW WinterthurCH 8401-Winterthur

# A Symposium under the Auspices of the DivisionChemical Research of the Swiss Chemical Society(SCS) and the Arbeitsgemeinschaft TheoretischeChemie (DBG, DPG, GDCh) with Conference ChairmenHans Peter Lüthi and Martin Quack (ETH Zürich) andJürgen Stohner (Zürich University of Applied SciencesWinterthur)

Introduction

The present Special Issue of CHIMIA isdevoted to the scientific subject as men-tioned in the title of this review and whichwas also the topic of a scientific meeting inGwatt, on the shore of Lake Thun in the fallof 2003. The 39th Symposium on Theoret-ical Chemistry (STC 2003) was the latest inan annual series of meetings with a long tra-dition in Europe and in Switzerland. In-deed, it was the tenth time that the meetingreturned to Switzerland with the followingprevious times, locations, and chairmen:1966 Zürich (Heinrich Labhart), 1969Spiez (Georges Wagnière), 1972 Genève(Laurens Jansen), 1976 Basel (Martin Jun-gen), 1980 Wildhaus (Klaus Müller), 1984Emmetten (Ulrich Müller-Herold), 1988Pontresina (Karl Lendi), 1994 Fiesch(Hanspeter Huber), 1998 Gwatt (WalterThiel). This time, the meeting was organ-ized by Hans-Peter Lüthi and Martin Quackfrom the Swiss Federal Institute of Technol-ogy (ETH) Zürich and Jürgen Stohner fromthe Zürich University of Applied SciencesWinterthur (ZHW) under the Auspices ofthe Division Chemical Research (DCR) ofthe Swiss Chemical Society (SCS) and the

Arbeitsgemeinschaft Theoretische Chemie(AGTC) of the Deutsche Bunsenge-sellschaft (DBG), the Deutsche Physikali-sche Gesellschaft (DPG), and the Ge-sellschaft Deutscher Chemiker (GDCh).About 170 participants attended the sympo-sium which offered 28 lectures of 45 mineach and two poster sessions with a total ofabout 125 posters. The main theme of themeeting STC 2003 is at the heart of the in-teractions of experiment and theory inchemistry, as the location was in the heartof Switzerland, near the capital and theBernese mountains (indeed, the AbstractBook included some basic history ofSwitzerland [1]). Molecular Spectroscopyhas always had a special relation to Theo-retical Chemistry, and the theme of themeeting follows an earlier one about adecade ago [2]. In the present short reviewwe introduce this special issue of CHIMIAby summarizing the lectures and some ofthe discussions of the meeting with fairlyextensive references, and thus this may al-so serve as a very compact review of thecurrent status of at least part of the field.This is then complemented by a small se-lection of papers from some of the invitedspeakers. It was not possible here to include


more for reasons of space and cost, but wehope that our review provides at least someinsight into those aspects not represented inthe following papers. These include at leastcontributions from several groups at Swissuniversities as well as one from Germanyand two from France. Given the theme ofthe meeting, there is an exceptional propor-tion of experimental work presented in sucha theoretical meeting, which led to manystimulating interactions.

Session 1

After a short welcome by the organizersand the chairman (Martin Quack) of Ses-sion 1, the meeting started already Sundayevening with an opening lecture by JürgenTroe, University of Göttingen (Fig. 1) on‘Reaction Dynamics with Wavepackets,Adiabatic Channels, and Classical Trajec-tories’. Whereas quantum scattering calcu-lations of inelastic collisions are most accu-rate, the numerical effort is prohibitive forlarger systems involving many atoms. Cap-ture rate constants dominate chemical ki-netics of barrierless reactions and statisticaltheories, such as the statistical adiabaticchannel model, have proven useful in thiscontext [3–5]. It has been demonstrated re-cently that the combination of classical tra-jectory calculations (with full quantumtreatment of the capture) with adiabaticchannel calculations describe capture rateconstants even down to very low tempera-tures (milli Kelvin) where quantum effectsare expected to be most prominent [6–9].Ingredients for the calculation of capturerate constants are potential energy surfaces,including for example ion-dipole interac-tions for charged reactants (e.g. O2

+ +

C8H10), permanent dipole and quadrupolepotentials, and adiabatic channels includingcentrifugal potentials. Jürgen Troe dis-cussed also certain reactions of great im-portance for the chemistry of the atmos-phere such as H + O2 (and isotopomericversions with D, T, Mu) and OH + OH. Inthe latter case, a global analytical potentialenergy hypersurface exists [10], and thespeaker pointed to the need for such poten-tial energy hypersurfaces for dynamicalcalculations. Beyond the technical aspects,he also provided the audience with a livelyjourney through time and history, mention-ing his early associations with the follow-ing speaker (Martin Jungen), the chairmanand some of the older members in the audi-ence, such as Tino Gäumann, who had notmissed the opportunity to join this event.

Martin Jungen, University of Basel(Fig. 2) talked on ‘What is a Muon Doing inAtoms or Molecules?’. The muon µ is an el-ementary particle belonging to the Leptonfamily. Its mass is about 207 times the massof the electron or about 11% of the atomicmass unit (≈0.11 u). It has a mean lifetimeof about 2.2×10–6 s. It decays into an elec-tron or positron plus neutrinos and exists asparticle and anti-particle (µ+ and µ–). µ+ canbe considered as a light proton, whereas µ–

could be termed a heavy electron. (µ+e–)can be considered a light isotope of hydro-gen (Muonium, Mu). In a theoretical study,‘exotic’ molecules have been investigatedwhich include one µ– particle: (ppµ–)+

(which would correspond to H2+),

(ααµ–e–)2+ (corresponding to He22+). Mar-

tin Jungen discussed various aspects ofbonding in these exotic systems as well asthe role of the Born-Oppenheimer approxi-mation [11]. He also mentioned the potentialimportance of (p+p+ µ–)+ for myonic fusion.

Session 2

This session chaired by Werner Kutzel-nigg, University of Bochum (Fig. 3) start-ed on Monday with a talk given by WimKlopper, University of Karlsruhe (Fig. 4)on ‘Explicitly-Correlated Calculations ofExcitation Energies’. The background ofthese techniques, which owe much to thechairman and the speaker himself in thissession, was lucidly introduced. Explicit-ly-correlated coupled cluster calculationsup to triple excitations are almost routinein high-quality ab initio studies of poten-tial energy hypersurfaces, energetic andspectroscopic quantities for moleculeswith less than six atoms [12]. The compu-tational accuracy reached demands to con-sider various corrections (e.g. relativisticspin-orbit and non Born-Oppenheimercorrections). Very large one-electron basissets are needed (with high orbital angular

Fig. 1. Jürgen Troe, Göttingen, explainingreactions lively with both hands, starting tomake a high flight in his lecture

Fig. 3. Werner Kutzelnigg, Bochum

Fig. 2. Martin Jungen, Basel, with a picture ofRobert Mulliken in the background, fromwhose famous lecture the title of MartinJungen’s lecture was adapted

Fig. 4. Wim Klopper, Karlsruhe, in his clearand highly instructive lecture


momentum quantum number l) which arecostly or even computationally prohibi-tive, simplified treatments are stronglyneeded to treat even larger molecules.CC2(R12) and CCSD(R12) are suitablemethods for larger molecules [13]. TheR12 method describes the Coulomb holeand the electron-cusp correctly by intro-ducing as a scaling factor the inter-elec-tron distance. However, this factor doesnot vanish for large electronic distances;with a Gaussian damping factor for thescaling efficient computational tech-niques with linear scaling can be used[14]. It has been demonstrated that excita-tion energies converge faster with CC2than with CCSD(T). Although excitationenergies of small molecules are close toexperiment [12], CC2(R12) has some-times difficulties with the symmetry ofthe excited state.

David Luckhaus, University of Göttin-gen (Fig. 5) reported on ‘Direct Multi-Arrangement Quantum Dynamics: FromDynamics to Reaction’ by presenting fullsix-dimensional quantum dynamics resultson HONO overtone spectroscopy and reac-tion dynamics [15–17].

A multi-dimensional potential energy(PES) and dipole moment hypersurface hasbeen obtained using density functional theo-ry (B3LYP functional, 6-311++G** basisset) in a ‘direct’ way without analytically fit-ting the ab initio data points. The data pointshave been interpolated using ‘successivelyaveraged spline interpolation’(SASI) to a de-sired grid size. Convergence of this proce-dure has carefully been checked. Luckhausinvestigated the cis-trans isomerization aswell as the hydrogen shift based on 6D vari-ational calculations of overtone spectra and6D wavepacket dynamics. Potential-opti-mized discrete variable representation (PO-DVR) combined with adiabatic contraction

has been used to obtain the OH overtonespectrum up to six quanta of OH-stretchingexcitation (about 22000 cm–1) for the two sta-ble HONO isomers. Numerous perturbationshave been identified and analyzed. In combi-nation with band intensities and intensity dis-tributions this allows a thorough understand-ing of intramolecular dynamics up to veryhigh vibrational excitations well into the vis-ible spectral region. He presented a new mul-ti-arrangement formulation of the dynamicsin local valence coordinates which allows todescribe tunneling in full dimensionality atvery high excitation. This provides a detailedpicture of the quantum dynamics for cis-HONO trans-HONO isomerization and of1,3-hydrogen transfer reactions.

Session 3

Session 3 was the first session devotedmostly to experiments and was chaired byPeter Botschwina, University of Göttingen,who introduced John P. Maier, Universityof Basel (Fig. 6) speaking about ‘Electron-ic Spectra of Carbon Chains: Relevance toAstrophysics and Nanoscience’.

Carbon chain radicals like CnH(2≤n≤8) can be found in dark interstellarclouds and ‘odd’ chains of the typeHC2n+1H are believed to exist in the inter-stellar medium. These ‘odd’ chains aremuch more reactive than the ‘even’ chainsHC2nH. The various compounds men-tioned are relevant for an understanding ofthe chemistry in interstellar medium. Verysensitive spectroscopic techniques (cavityring-down spectroscopy with supersonicjet expansions [18][19], recently extendedby the Basel group to treat ions [20], aswell as frequency modulation absorptionspectroscopy) are needed to examine thosecompounds in the laboratory which then al-

lows to identify carbon chains throughtheir electronic absorption spectrum. Theodd chains are more reactive and short-lived and are investigated by mass-selec-tive resonant two-photon ionization tech-niques (R2C2PI, [21]). Understanding theelectronic spectra poses a challenge to the-ory since one would require line positionsto better than 1 cm–1 for the carbon chainabsorptions between 400 and 800 nm. Suchaccuracy can hardly be reached by pure abinitio theory to date for such molecules.Thus, laboratory spectroscopy must helpout at present. Another important quantityis the oscillator strength which togetherwith accurate line positions would facili-tate the assignment of electronic spectra indark molecular clouds (temperature about10 K, 104 particles per cm3) and diffuse in-terstellar clouds (temperature about 100 K,102 particles per cm3). An investigation ofelectronic transitions A 1∆u←X 1Σ+

g and B1Σ+

u ←X 1Σ+g as a function of chain length

4≤n≤7 (HC2nH) shows that the A-B stategap is far from zero (which would be ex-pected for a one-dimensional crystal) evenfor the rather long HC14H chain (gap ofabout 2 eV). Those investigations may al-so be used to test or calibrate models ofmolecular electronic devices [22].

Frederic Merkt, ETH Zürich (Fig. 7)reported on ‘High-Resolution VUV Spec-troscopy, Rydberg States and Cations’ withrare gas dimers (Ar2

+) as examples. Poten-tial energy functions for six electronicallyexcited states have been derived from high-resolution photoelectron spectroscopy withan accuracy of 0.06 to 2 cm–1 [23]. F. Merktthen pointed to new developments from hisgroup allowing for high resolution of 0.008cm–1 in the VUV. The derived potential en-ergy functions agree reasonably well withthose calculated ab initio. Accurate mea-surements of the hyperfine structure in 83Kr

Fig. 5. David Luckhaus, Göttingen Fig. 6. John P. Maier, Basel, with a model of along carbon chain molecule in one hand

Fig. 7. Frederic Merkt, Zürich, explainingsome of the special properties of Rydbergstates


by pulsed-field ionization techniques (nsand nd Rydberg states with the principalquantum number n ranging from 30 to 190)revealed nuclear spin dependence of the ap-pearance of the Rydberg state spectra, espe-cially at high n, that leads to hyperfine split-tings. Multichannel quantum defect theory(MQDT) is adequate to explain the ob-served features [24]. A more completeaccount of his lecture and related workappears in this issue of CHIMIA [25].

Session 4

This session was in turn devoted to the-ory with Wilfried Meyer (Fig. 8, Universityof Kaiserslautern) as chairman and startedwith a talk by Hans-Joachim Werner, Uni-versity of Stuttgart (Fig. 9) on ‘Explicitly-Correlated Total Wavefunctions: LMP2-R12 with Density Fitting’. High-level elec-

tronic structure calculations suffer fromstrongly non-linear scaling with systemsize and with size of the atomic basis set.The calculation of 2-electron integrals andtheir transformation is a true bottleneck.Although electron correlation is importantfor high-quality calculations, it convergesrather slowly with basis set size (orbitalangular momentum quantum number l).Local density fitting (LDF) proceduresstrongly enhance convergence.

LDF-MP2 [26] and LDF-CCSD [27]scale linearly with molecular size. A costlypart of the calculation is the four-index in-tegral evaluation due to its unfavorablescaling with respect to atomic basis set size.Density fitting is able to change this scalingconsiderably by introducing individual ex-citation subspaces (domains; their size isindependent of the size of the molecularsystem) for electron pairs and a multipoleexpansion for the generation of the 2-elec-tron integrals for distant pairs. Different fit-ting bases for each electron pair can resultin scaling down to N as compared to N3

(with N the atomic orbital basis set size).The optimization of methanol pentamerand t-butanol pentamer structures is feasi-ble and LMP2 is probably faster than DFT.A LDF-MP2 combined with R12 is mostdesirable.

Jeppe Olsen, University of Aarhus (Fig.10) reported on ‘Coupled Cluster Expan-sions with Quadruple and Higher Excita-tions’ to calculate accurate thermochemicaland spectroscopic data, in particular atom-ization energies and harmonic vibrationalfrequencies [28][29]. With increasing qual-ity from CCSD(T) (perturbative triple exci-tations), CCSDT, CCSDTQ (quadruple ex-citations) to CCSDTQ5 (quintuple excita-tions), atomization energies of diatomicscan be calculated with an accuracy of about0.5 kJ/mol (in case of N2 with CCSDTQ5).Olsen discussed a number of difficult casessuch as F2, C2H4, HOF and O3. It is impor-tant to include all electrons in the correla-tion treatment as well as using core valencebasis sets, which, however, need to be verylarge (up to quintuple-zeta quality). Smallerrors in the atomization energies obtainedwith CCSD(T) are fortuitous due to errorcancellation. The outstanding lecture ofJeppe Olsen actually stimulated some dis-cussion on how to best compare very accu-rate ab initio results with spectroscopic ex-periments, a question of obvious interest ingeneral and for the mixed audience repre-sented here in particular. For instance, oneway would be to compare indirectly ob-tained ‘experimental’ re-structures with thedirectly obtained ab initio equilibriumgeometry. Another possibility would be tocalculate theoretical transition frequenciesusing a full potential and rovibrational dy-namics, a routine method for diatomic mol-ecules, but difficult for polyatomic mole-

cules. Also the data set would become verylarge and not transparent in the case ofpolyatomic molecules. An intermediateprocedure would be to do full dimensional(or high dimensional) calculations on ap-propriate potential energy hypersurfacesfor line frequencies and fit these using spec-troscopic effective Hamiltonians with re-duced parameter sets. This may perhaps bethe most meaningful approach, which iscertainly feasible for diatomic moleculesand it was also pointed out that such proce-dures were already used for polyatomicmolecules [10][30–36] even though some-times with accuracy limited by the multi-dimensional Quantum Monte Carlo tech-nique or by reduced dimensionality treat-ments. Further discussion of this importantmatter followed later in the lectures by K.Hirao, W. Thiel, and J. Gauss.

Session 5

The next session was chaired by JürgenHinze, University of Bielefeld (Fig. 11) andthe opening talk was given by GernotFrenking, University of Marburg (Fig. 12)entitled ‘The Nature of the Chemical Bond– Old Questions, New Answers’. He dis-cussed the ability of molecular orbital(MO) and valence bond (VB) models to ra-tionalize the physical origin of the chemicalbond in relation to heuristic bonding mod-els as presented in chemistry textbooks.However, as Frenking pointed out, these of-ten neglect knowledge on the physical ori-gin of the chemical bond gained in theoret-ical studies by Hellmann, Hirshfeld, Rue-denberg, Kutzelnigg, Schwarz and others.The basis of his work goes back to the en-ergy decomposition schemes proposed byZiegler [37] and Morokuma [38] in the 70s.Frenking reviewed the Energy PartitioningAnalysis (EPA) addressing a correct parti-tioning of the energy in order to describe

Fig. 8. Wilfried Meyer, Kaiserslautern, aschairman

Fig. 10. Jeppe Olsen, Aarhus, explaining thedifficulties of highly accurate calculations

Fig. 9. Hans-Joachim Werner, Stuttgart,giving a thoughtful reply to a question


the electrostatic or covalent nature of thebond. Particular attention was given to therole of electrostatic attraction and Pauli re-pulsion which, following Frenking’s ideas,have to be considered separately, these be-ing two well-defined terms with a clearphysical meaning. Besides the brief intro-duction to the approach he presented aconsistent number of examples, mainlymetal complexes and molecules of maingroup element systems, where new an-swers were given. A recent discussion ofthese subjects from Frenking and cowork-ers can be found in [39] and [40]. Thechemical bond being central to theoreticalchemistry a long discussion followedFrenking’s presentation.

Kimihiko Hirao, University of Tokyo(Fig. 13) held the PCCP lecture sponsoredby the journal Phys. Chem. Chem. Phys.The title of his lecture was ‘Recent Ad-vances in Electronic Structure Theory’.Third-order Douglas-Kroll (DK3) coupledcluster methods have been used up to con-

nected quadruple substitutions. Hirao re-ported spectroscopic quantities like rota-tional constants (accurate to about 0.02cm–1), vibration-rotation interaction con-stants (accurate to about 0.01 cm–1), har-monic vibrational frequencies (accurate toabout 8 cm–1), and dissociation energies(accurate to about 0.02 eV) for hydrides ofthe second to the fifth row of the periodictable [41]. DK3 results are almost compara-ble to solutions obtained by solving theDirac equation. Furthermore, the relativestability of three SiC3 isomers has been de-termined by second-order perturbation the-ory with multiconfigurational self-consis-tent field reference functions (GMC-PT).The results obtained by this method con-firm the earlier relative stability as reportedby Fritz Schaefer’s group [42].

Session 6

The Tuesday morning’s Session 6 start-ed with the Hellmann Prize award ceremo-ny chaired by Walter Thiel (MPI Mülheim)as chairman of the Arbeitsgemeinschaft fürTheoretische Chemie (AGTC). Traditional-ly, the name of the prize winner is kept con-fidential until the award ceremony and heappears as speaker N.N. in the conferenceprogram. Only some participants mighthave noticed that, while an abstract for thelecture N.N. did not appear among the lec-ture abstracts at the beginning of the ab-stract book, there was one abstract on page145 in the later collection of contributed pa-pers where the footnote ‘poster’ was miss-ing, indicating either a misprint – or elsethat this was the missing Hellmann Prizelecture. Indeed, Georg Kresse, Universityof Vienna (Fig. 14) received this prize forhis contributions to developing and effi-ciently implementing plane wave densityfunctional methods allowing simulations ofsolids and solid surfaces (see homepage of

the AGTC at http://www.agtc.uni-bonn.deand [43]).

In his lecture on the ‘Importance of Sin-gle-Electron Energies for the Description ofCO Adsorption on Surfaces’ he discussedthe failure of semilocal density functionalsin properly describing the stable adsorptionsite of CO on Pt(111). This failure is ration-alized by investigating the interaction of thehighest occupied molecular orbital (HO-MO) and the lowest unoccupied molecularorbital (LUMO) of CO with the platinumsurface and it points to a deficiency in thepresent local and semilocal functionalswhich leads to an underestimation of theHOMO/LUMO gap. Functionals which arecorrected for self interaction or which in-clude Hartree-Fock exchange seem to bet-ter describe the experimental findings[44][45]. This lecture as well stimulatedquite some discussion on various densityfunctional approaches, as also on the possi-ble need for treating nuclear motion as wellby quantum dynamics.

The following lecture by Rainer D.Beck, EPF Lausanne (Fig. 15) dealt withexperiments on molecule surface interac-tions [47][46]. He addressed the ‘Vibra-tional Mode-Specific Reaction of Methaneon a Nickel Surface’. Beck reported exper-iments on state-resolved sticking coeffi-cients for vibrationally excited CH4 on asingle crystal nickel surface. The methanechemisorption reaction is a prototype forthe activated dissociative chemisorption ofa polyatomic molecule. The experimentalsetup involves the generation of a molecu-lar beam of methane prepared in specific vi-brationally excited states and the determi-nation of the chemisorption products afterthe impact with the metal surface usingAuger electron spectroscopy. With thesetools the Lausanne group contributed to thedebate on whether the chemisorption reac-tion of CH4 on a Ni(100) surface is statisti-

Fig. 11. Jürgen Hinze, Bielefeld, one of thesenior chairmen of the field and this meeting

Fig. 12. Gernot Frenking, Marburg

Fig. 13. Kimihiko Hirao, Tokyo, the PCCP lec-turer of this meeting

Fig. 14. Georg Kresse, Vienna, this year’sHellmann Prize winner


cal or mode-specific. It has been shown thatthe latter is indeed the case as it was foundin the gas-phase reactivity of methane. Amore complete account of this work is pro-vided in the present issue [46].

Session 7

Session 7, which was chaired by Hans-Peter Lüthi, ETH Zürich, was opened by alecture by Roberto Marquardt, Universityof Marne-La-Vallee (Fig. 16) entitled ‘Vi-brational and Rotational Wave Packet Mo-tion in Polyatomic Molecular Systems’ andincluded actually both the theory of gas-phase isolated molecule dynamics andgas–surface interactions. Within the spec-troscopic approach for the calculation ofthe time-dependent quantum dynamics inpolyatomic molecules he discussed how todetermine global potential energy and di-pole moment surfaces. Being a prototypefor chemical reactions and adsorption

processes, the laser-assisted inversion ofammonia was the main subject of his lec-ture. With the help of a detailed investiga-tion of the vibrational wave packet motionin a four-dimensional treatment of the time-dependent excitations and intra-moleculardynamics, he analyzed the roles of the var-ious mechanisms for the inversion motionof highly vibrationally excited ammoniamolecules. In particular he showed thateven at energies well above the inversionbarrier, the dominating process is still tun-neling when compared with the less com-petitive intra-molecular vibrational redistri-bution and direct excitation [48]. The basiccomponents of these studies are the intro-duction of the concept of the infrared NHchromophore as the group of NH stretchingand bending vibrations in NHXY com-pounds which in turn allows for the defini-tion of a 4-dimensional subspace and thecalculation of vibrational eigenfunctionsand eigenvalues within this 4D space usingWatson’s Hamiltonian. Details on a globalelectric dipole function of ammonia can befound in [49]. The last part of the talk wasdedicated to the role of rotations and molec-ular orientation. The lecture included aswell some very thoughtful comments on theconstruction of potential hypersurfaces forgas molecule–surface interactions and amore complete account can be found in thisissue [50].

Quantum computing was one of themain subjects of Regina de Vivie-Riedle’s(Universität München, Fig. 17) talk. While‘quantum algorithms’ have been alreadypublished only few ‘qubit machine’ imple-mentations are available at a laboratory lev-el. In this talk we heard about new physicalimplementations which involve vibra-tionally excited molecules. Beside comput-ing and information storage devices the ap-proach involved different tools from thetheory of spectroscopy and dynamics ofmolecules. In first place we are in the rangeof ultrafast molecular processes [52] whichare also of interest in chemical or photo-physical reactions dynamics [34][51]. Con-trol of these processes is then required andcan be reached using coherent laser lightand specially designed laser pulse shapes.De Vivie-Riedle showed how a basic con-trol tool (the ‘Optimal Control Theory’(OCT) [53][54]) can be extended and usedto find the optimal laser field to manipulatecomplex molecules. Regina de Vivie-Riedle presented data and examples for anew quantum computer implementation.The main quantum chemical data were ex-tracted from HF, CIS, DFT and TDDFT cal-culations which are suited for large molec-ular frames and allow for a setup of com-plex embedded systems (see for examplethe Wesolowski talk). Regina de Vivie-Riedle also discussed electrocyclic reac-tions as molecular switches, where in the

discussion the point was brought up thatchiral molecules had been calculated fortheir use as femtoseconds switches [55]. Al-together the work presented opens avenuesto an interesting research field.

Session 8

Dirk Schwarzer, University of Göt-tingen (Fig. 18) was Chairman of Session 8. Samuel Leutwyler’s (University ofBerne, Fig. 19) lecture on an experimentaltopic touched on another fundamentalsubject: Hydrogen bonds which play animportant role in biology and chemistry[56]. He showed that in a 7-hydroxyquino-line⋅(NH3)3 cluster (7HQ⋅(NH3)3) a singleH atom transfer can be induced along theammonia wire. In particular after initiationvia S1←S0 excitation the reaction does notproceed directly from the vibrationalground state of the S1 state but additionalexcitations are required to activate the H-transfer reaction. CASSCF with a 6-

Fig. 15. Rainer D. Beck, Lausanne

Fig. 16. Roberto Marquardt, Marne-La-Vallee

Fig. 17. Regina de Vivie-Riedle, München. Ina fresh and smiling presentation.

Fig. 18. Dirk Schwarzer, Göttingen


31(+)G(d,p) basis set was used to rational-ize and predict experimental data obtainedperforming laser UV analysis after havingsynthesized and cooled the 7HQ⋅(NH3)3clusters in a 20 Hz pulsed supersonic jet ex-pansion of Ne mixed with 1% NH3. A moredetailed report on this subject can be foundin [57] and in this issue a summary reportappears as well [58].

Hydrogen bonding is also one of the re-search subjects of Martina Havenith,Ruhr-Universität Bochum (Fig. 20) who re-ported on two spectroscopic measurements:a gas-phase disaccharide and the fully ana-lyzed gas-phase high-resolution IR spec-trum of the formic acid dimer. There is ex-perimental evidence for double protontransfer tunneling in formic acid dimer [59]which is a prototype for double hydrogenbonded organic complexes. Havenith’sgroup fully resolved the tunneling splittingand determined a ground-state tunnelingfrequency of 86 MHz and a C-O vibra-tionally excited state tunneling–frequencyof 300 MHz. The experimental procedure

involves the formation of the clusters in asupersonic jet expansion and spectroscopicmeasurements using a lead salt diode laser.Beside the importance of these data for bi-ological studies she underlined the lack ofreliable theoretical models for these sys-tems. There was some discussion on the un-successful search for imaginary frequenciesin the alleged transition state and the exis-tence of an open formic acid dimer with on-ly one hydrogen bond, postulated before onthe basis of kinetic and spectroscopic evi-dence [60][61].

Session 9

As chairman of Session 9, Eugen H.Schwarz, University of Siegen (Fig. 21) in-troduced Marius Lewerenz University ofParis (Fig. 22) who continued his series ofstudies on hydrogen bonds. In particular hepresented IR spectroscopic results for thehydrogen-bonded dimers thiirane-HF andthiirane-DF whose analysis has revealed aglobal anharmonic coupling between alllow frequency intermolecular modes andthe high frequency HF/DF stretching mode.He pointed out that commonly used theo-retical models might not be sufficient forthe calculation of the red shift induced bythe formation of the hydrogen bond and hepresented results from an anharmonic andmultidimensional theoretical treatment ofthe vibrational dynamics obtained over apart of a complete ab initio potential ener-gy surface. In the second part of his talk, M.Lewerenz addressed very weakly boundvan der Waals complexes. The target sys-tem was the (NeHen)+ cluster class as ex-ample for a successful application of Quan-tum Monte Carlo sampling combined witha diatomics in molecules (DIM) approach.The calculations reveal the existence of a stable symmetric triatomic ion core (He-Ne-He)+. A detailed summary of this

work can be found in the present issue ofCHIMIA [62].

Walter Thiel, MPI Mülheim (Fig. 23)reviewed the state of the art in the theoreti-cal approaches to obtain spectroscopic pa-rameters from ab initio calculations. Thekey step of the method includes the compu-tation of harmonic and anharmonic forcefields followed by a rovibrational perturba-tion treatment. He presented the applicationof this approach to a series of small reactivemolecules and discussed the results withparticular attention to the convergence ofthe theoretical methods [63]. The secondhalf of the talk addressed variational calcu-lation on ammonia molecule [64] whichwas repeatedly a topic at the meeting[48–50][65]. The method chosen for thecalculation of the PES was coupled clusterCCSD(T) with extrapolation to the com-plete basis set. Thiel showed that it is pos-sible to systematically obtain results just afew cm–1 away from experimental data ifappropriate tools are used. He underlinedthat corrections (for example to account for

Fig. 19. Samuel Leutwyler, Bern

Fig. 20. Martina Havenith, Bochum

Fig. 22. Marius Lewerenz, Paris

Fig. 23. Walter Thiel, MülheimFig. 21. Eugen H. Schwarz, Siegen


relativistic effects) are required and thatparticular attention should be paid to the ac-curacy of the calculation at every singlestep of the procedure. A more completesummary of this work can be found in thisissue [66].

Session 10

The Chairman of Session 10 wasFrédéric Merkt, ETH Zürich (Fig. 7). Theimage of handshaking molecules was ap-propriately given by Martin Suhm, Uni-versity of Göttingen (Fig. 24) in his talkabout chiral recognition and self-recogni-tion. Chiral recognition is well known toplay a key role in biochemical processesand organic synthesis and Suhm exploredthis field with a systematic study whichinvolved the combination of theoreticaland experimental spectroscopic tech-niques. The presented chemical systemsare for example glycidol [67], closely re-lated to the important oxirane-carbonitrile[68] which has been studied for biochem-ical selection in evolution and parity vio-lation, and lactates [69] where the chiralself-recognition (i.e. the ability of a mol-ecule to distinguish between a copy or amirror copy of itself) arises from inter-molecular interactions mainly due to hy-drogen bonds. Weak secondary interac-tions, involving for example CH-O, werealso the subject of interest for the deter-mination of chiral discrimination. Themain experimental data are obtained viaRagout-jet FTIR spectroscopy (a rapid-scan FTIR supersonic jet technique) thathas evolved to a very efficient techniqueover the years [70][71]. The experimentalresults were rationalized with quantumchemistry calculations [72][73].

Tomasz A. Wesolowski, University ofGeneva (Fig. 25) gave a lecture entitled‘Electron Density Partitioning as a RouteTowards Accurate Multi-Scale Modeling ofComplex Molecular Systems and Materi-als’. He presented the recent theoretical de-velopments and applications of a densityfunctional theory approach, which is basedon the so-called total energy bi-functionalE[ρA,ρB] already used in early work byGordon and Kim and developed to a pow-erful tool by Wesolowski and his group forcomputer modeling of complex polyatomicsystems at quantum mechanical level. Heexplained that in this approach the effectivepotential coupling of two subsystems is ex-pressed in the orbital-free embedding for-malism [74][75]. This formalism allows the

calculation of electronic-structure-depend-ent properties of an embedded subsystemwithout the construction of the wavefunc-tion of the whole system comprising themolecule under investigation and its micro-scopic environment (for example an atomin a solid, molecule in a solvent, moleculein a porous material or molecule on a sur-face). Then he also reviewed some chal-lenging issues of density functional theory(DFT) such as approximating the kineticenergy functional or describing weak inter-molecular interactions (e.g. Ne-Ne, Ar-Ar).He noted that these are of particular signif-icance for practical applications of the or-bital-free embedding formalism. In the lastpart of his lecture he mentioned a recent ex-tension of this formalism, which allowseven the study of localized excited states ina condensed phase. A more detailed sum-mary appears in the present issue [76].

Session 11

This session was chaired by KimBaldrige, University of Zürich (Fig. 26),

who introduced Joachim Sauer, Hum-boldt-Universität, Berlin (Fig. 27) giving alecture with the title ‘Calculations on Tran-sition Metal Oxides –From Gas Phase Clus-ters to Solid Catalysts’. In the first part hetalked about theoretical investigations ofvanadium oxides as selective catalyst forpartial oxidations. Vanadium oxides areparticularly interesting because their reac-tivities show a dependence on the aggrega-tion level [77][78]. As model systems a thinfilm of V2O5 on e.g. α-Al2O3 or SiO2 isused. He presented calculations of the ener-gy profile for the selective oxidation ofmethanol to formaldehyde [79][80]. Thisreaction has the advantage that it is well in-vestigated experimentally with solid vana-dium oxide as a catalyst as well as in the gasphase for the related molecular cation (withmass spectrometry). The correspondingcalculations show large differences in reac-tivity between cationic gas phase speciesand neutral clusters and support the experi-mental results. He discussed the reliability

Fig. 24. Martin Suhm, Göttingen, with left andright hands in almost symmetric positions

Fig. 25. Tomasz A. Wesolowski, Geneva

Fig. 26. Kim Baldrige, Zürich University

Fig. 27. Joachim Sauer, Humboldt UniversityBerlin


of DFT for the description of theoxygen–metal bond and the activation bar-rier. He mentioned that the methanol oxida-tion is one of the rare examples where DFTcalculations (with PW91 or B3LYP func-tionals) yield too-high reaction barriers.Some evidence was found that this iscaused by the biradical character of thetransition state for this system [81].

This day of the conference closed witha lecture by Claude A. Daul, University ofFribourg (Fig. 28) entitled ‘Modeling Mag-netic and Spectroscopical Properties of Co-ordination Compounds’. He reported recentresults on a new DFT-based ligand fieldmodel and its application to study magnet-ic and spectroscopic properties of coordina-tion compounds including investigations ofhis group on a first principle study of thenephelauxetic effect. They comparedRacah’s parameter A and B for the free met-al ions with the corresponding values in a

crystal field. He mentioned that in such in-vestigations the covalent reduction increas-es with increasing transition metal oxida-tion state in the series CrO4

4–, Mn O44–,

FeO44– and with an increasing metal-ligand

bond covalency in the series CrX4 (X = F,Cl, Br, I). He further showed that this ap-proach can also be utilized for magnetic ex-change coupling in homonuclear transitionmetal dimer complexes. This approach isbased on a model of localized d-electronsand on a procedure allowing to express itsparameters in terms of exchange andCoulomb integrals from DFT calculationsof a homonuclear dimer complex. He de-scribed how it is possible to relate these in-tegrals with the manifold of all Slater deter-minants of the active space originatingfrom the magnetic electrons of the dimer.This method has been successfully appliedto d(9) and d(1) model clusters involvingCuII and Ti2Cl9

3–. He further mentionedthat his group was also able to extend this

approach to cases with more than one un-paired electron per site. A more detailedsummary of this research can be found inthe present issue of CHIMIA [82].

Session 12

Jürgen Stohner, ZHW Winterthur (Fig.29) was chairman of Session 12, the firstsession of the last day, introducing JürgenGauss, Universität Mainz (Fig. 30), wholectured on ‘Rovibrational Spectroscopyand Quantum Chemistry’. He demonstratedthe fruitful interplay between high-levelquantum-chemical calculations and experi-mental rovibrational spectroscopic investi-gations. Spectroscopic parameters (e.g. ro-tational constants, equilibrium structure androtation-vibration interaction constants)from high-level quantum chemical calcula-tions are an extremely helpful starting pointfor the analysis of complex experimentalrovibrational spectra. He explained thatwithin a perturbational approach to thespectroscopic problem modern analytic de-rivative techniques for general coupledcluster models in combination with largebasis sets can provide the required spectro-scopic constants in a very efficient way. Hediscussed some of the problems that arisewhen relating the experimental ground staterotational constants to molecular structuralparameters. The standard approach for poly-atomic molecules is to determine spectro-scopic ground state rotational constants B0for several isotopomers of the molecule andto relate these constants to their equilibriumvalues Be or else determine vibrational statedependent Bv and extrapolate these to B0,but this becomes an increasingly difficulttask for larger molecules and increasingnumber of degrees of freedom. The difficul-ties related to the determination of the ex-perimental vibration-rotation interaction

constants may be overcome by using con-stants obtained from electronic structurecalculations. Gauss showed that the vibra-tion–rotation interaction constants are smallcompared to the ground state rotational con-stants and may be calculated with relativelyhigh accuracy. High-quality equilibriumstructures may therefore be obtained usingexperimental rotational constants and calcu-lated vibration–rotation interaction con-stants [83]. He also reported investigationson the magnitude of various sources of er-rors in empirical equilibrium structureswhen the vibration–rotation interaction con-stants were calculated at various standard abinitio wave function/basis set levels. Hestated that empirical equilibrium bondlengths have a relative accuracy of the orderof 10–3 when the vibration–rotation interac-tion constants were calculated at a correlat-ed level of electronic structure theory. He il-lustrated this successful interplay of theoryand experiment on the examples of H2C2and F-C4-H. As a most impressive examplehe reported quantum chemical predictionsof the rotational spectrum of HSOH [84],which led to its infrared and microwavespectroscopic detection in the gas phase.Jürgen Gauss’s very stimulating lecturegave rise to considerable discussion amongspectroscopists and theoreticians. Some ofthis expanded on the points already raised inthe discussions of the lectures by Olsen, Hi-rao and Thiel, in particular. Botschwinapointed to some earlier theoretical work onfluoroacetylene [85] and it was pointed outas well that some experimental detection ofHSOH had been reported [86] as well as abinitio and mode selective tunneling calcula-tion on various HSOH isotopomers, includ-ing even parity violation in this molecule aspart of a larger series of chiral HXYH mol-ecules [87][88].

The following lecture was given byMarkus Reiher, Universität Erlangen (Fig.31) on ‘Mode-Tracking: A New Method for

Fig. 28. Claude A. Daul, Fribourg

Fig. 29. Jürgen Stohner, Winterthur andZürich

Fig. 30. Jürgen Gauss, Mainz


the Calculation of Pre-Selected MolecularVibrations’. He started his lecture by men-tioning that the quantum chemical standardapproaches for the calculation of vibrationalspectra are usually limited to small mole-cules. To overcome this problem the so-called mode-tracking approach was devel-oped for the accurate normal mode calcula-tion of a pre-selected molecular vibration,which is important in the experimental spec-trum, for instance, in a very large molecule.The vibrational eigenvalue problem issolved in a small subspace of the completenormal coordinate space and one or a coupleof predefined modes are projected out of all3N modes of the molecule. He mentionedthat this is a great benefit since the calcula-tion of the full Hessian is not necessary andtherefore comparatively little computationaleffort is needed compared to the ‘standard’procedure. He discussed some computation-al details, stating that for a good convergencebehavior of the method it is important to gen-erate a sufficiently accurate guess for the de-sired normal modes and for the precon-ditioner. This guess should be based on aquantum chemical method, which is compu-tationally less expensive than the methodused for the subspace. Therefore one canchoose even semiempirical methods.Markus Reiher mentioned that with thisapproach, it is possible to study relativelylarge molecules, for example: single–walledcarbon nanotubes, large metal complexes orSchmidbaur’s cluster [89–91].

Session 13

Ralph Jaquet (Universität Siegen)chaired Session 13 with two further theoret-ical highlights. Lorenz S. Cederbaum, Uni-versität Heidelberg (Fig. 32) introduced hiscontribution with the title ‘IntermolecularDecay and Ultrafast Energy Transfer inClusters and Weakly Bound Systems”. He

pointed out that with large scale ab initio cal-culations it is possible to study the relaxationof molecular clusters after excitation by in-ner-valence ionization. He reported thatelectronically excited cations relax in gener-al by dissociation and photon emission. Au-toionization is forbidden for energetic rea-sons. The situation changes fundamentallyin an inner-valence ionized cluster, which re-leases its excess energy by emitting an elec-tron. This newly discovered and analyzedprocess, referred to as IntermolecularCoulombic Decay (ICD) [92–94], is charac-terized by an inner-valence hole state in aweakly bonded system which can undergoultrafast relaxation on a femtosecond timescale due to energy transfer to a neighboringatom, followed by electron emission fromthis neighboring site. He discussed theoreti-cal methods which were developed to pre-

dict properties (e.g. lifetimes) of molecularsystems undergoing electronic decay. Theseapproaches allow the study of the relaxationprocess of inner-valence holes in clusters.He noted that for Ne clusters strong experi-mental evidence was recently found for anICD process [95], which was theoreticallypredicted [92]. He concluded that the under-lying ICD process is of a very general natureand it has consequences far beyond clustersand single ionization.

The last morning lecture was given byWilliam H. Miller, University of Califor-nia/Berkeley (Fig. 33) who spoke about theuse of ‘Semiclassical Theory to IncludeQuantum Effects in Classical MolecularDynamics Simulations’. Bill Miller startedhis lecture with a summary of theoreticalchemical dynamics. Clearly, quantum dy-namics is, in principle, required and it isfeasible for small molecular systems. It pro-vides state to state reactive scattering tran-sition probabilities and cross sections, timeevolution of wave packets and direct quan-tum calculation of chemical reaction rates,

the latter being a major development fromMiller himself. Many examples for triatom-ic systems A + BC, and four atomic systemsAB + CD exist, the latter constituting aboutthe limit in size of the current state of the artin this field. The second widely used ap-proach is classical molecular dynamics ei-ther on empirical potential hypersurfaces(‘force fields’) or ab initio potential hyper-surfaces (such as the density functional the-ory ab initio molecular dynamics followingCar and Parrinello). This approach is feasi-ble for complex systems including proteinsand the like, but nuclear dynamics is treat-ed here with 17th century science. Thequestion is then, how to introduce quantumeffects. Basically three strategies are in use(i) Ignore them! (ii) Treat a few degrees offreedom quantum mechanically and the re-maining ones classically (iii) Treat all de-

grees of freedom semiclassically. It is thethird strategy that was further pursued inMiller’s lecture. While the basis semiclassi-cal approximation can be found in work ofVan Vleck from 1928, the renaissance ofthis field is largely due to Miller’s workabout three decades ago [96]. Semiclassicaltheory provides in general a good descrip-tion of essentially all quantum effects inmolecular dynamics, e.g. interference andcoherence, tunneling, vibrational zero pointenergy, effects of identical particle symme-try or quantization of bounded motion. Forsmall molecules, this has been appreciatedand checked by many applications in thepast. Miller presented several examples. Heconcluded that in principle it should be pos-sible to use the semiclassical theory to addin an approximate way quantum effects toclassical simulations of chemical reactionsin solution, clusters and proteins in com-plex molecular systems. Quantum effectsare added, he explained, by replacing theboundary value problem of semiclassicaltheory by an average over the initial condi-

Fig. 31. Markus Reiher, Erlangen

Fig. 32. Lorenz S. Cederbaum, Heidelberg Fig. 33. William H. Miller, Berkeley


tions of classical trajectories. He then con-tinued with an practical implementation ofthe semiclassical theory for such complexsystems which is based on initial value rep-resentations. He reviewed in the last part ofhis talk the basic ideas of such approachesand described the broad spectrum of appli-cations for a number of chemical problems(for a recent overview see [97]). Amongother things Bill Miller’s lecture providedan illustration that even in the days of lap-tops and power point, some of the most bril-liant theoretical lectures can be presentedusing hand-written transparencies.

Session 14

The final session was chaired by Do-minik Marx, University of Bochum (Fig.34). The first contribution to this sessionwas by Nikos L. Doltsinis (Ruhr-Univer-sität Bochum) with an instructive talk on‘Excited State Tautomerism of the DNABase Guanine’. He introduced this subjectwith the fact that although up to six tau-tomeric forms of guanine coexist in IR-UVspectroscopic molecular beam experiments,only one, the so-called N9H-keto tautomeris usually present in healthy DNA. For boththe interpretation of the experimental dataand to elucidate the biological relevance ofthe N9H-keto form his group investigatedtheoretically the photophysical properties ofthe guanine tautomers. For such investiga-tions they used a density functional restrict-ed open-shell Kohn–Sham approach [98].He presented results which show that thereare large variations in the extent of structur-al relaxation in the S1 (ππ∗) excited state fordifferent guanine tautomers [99]. The ketoforms have larger geometric changes uponelectronic excitation to the S1 state than theirenol counterparts. Then he further pointedout that methylation of nitrogen N9 in gua-

nine constitutes an important step towards‘real’ biological systems, since this is just inthe position of the backbone linkage inDNA. Their current studies suggest that dueto heavy structural distortions in the S1 statethe S1←S0 transition probability of this par-ticular tautomer is rather small. Car-Par-rinello calculations [100–102] have demon-strated that large structural changes in 9Me-keto guanine also result in significantlyshorter internal conversion times. Then hesummarized their findings for this simplemodel system and its implications for thephotophysical properties of DNA buildingblocks. He proposed that, apart from a shortexcited state lifetime, low absorption prob-ability of the isolated nucleobase may con-tribute to protecting DNAfrom UV damage.These mechanisms may be exploited in fu-ture synthesis of photostable biomolecules.

The final lecture of the symposium wasgiven by Michele Parrinello, ETH Zürichand Swiss Center for Scientific Computing(CSCS), Manno (Fig. 35) entitled ‘Calcula-tion of Free Energy Surfaces in Classicaland ab initio Molecular Dynamics’. Hestarted his lecture by explaining that at leastby now he was moving from Newton toGibbs (in reply to a comment in BillMiller’s lecture). The free energy surface ofcomplex systems is usually characterizedby the presence of deep minima separatedoften by large barriers. The transitions oversuch barriers correspond to chemical reac-tions and conformational changes. He ex-plained that the direct simulation of theseprocesses is often not possible because ofthe exponential dependence of the rates onthe barrier height (this means that the freeenergy minimum near the start configura-tion will eventually not be left). This resultsin a severe time scale problem. Then he in-troduced his ‘metadynamics’ method forexploration of the properties of the multidi-mensional free energy surfaces of complex

many-body systems by means of a coarse-grained non-Markovian dynamics in aspace defined by a few collective coordi-nates. He explained that the characteristicfeature of this dynamics is the presence ofa ‘history’-dependent potential term that,in time, fills the minima in the free ener-gy surface. This allows a very efficient ex-ploration of the free energy surface as afunction of the chosen collective coordi-nates. Then he presented as a demonstra-tion of the power of this approach someimpressive examples including simula-tions of some fundamental real-life chem-istry such as Na+ and Cl– in water or NO3

–

reduction to NH3 by pyrite, which takesplace in oceanic hydrothermal vents andmay be important in early evolution.Some of the work reported in this lectureis published in [103–105].

Posters

The posters of this meeting were numer-ous and reflected upon the areas treated inthe lectures, including however also furtherareas of research. The poster sessions led tovery lively scientific discussions, althoughsome participants noted a certain lack ofbeer that might have increased the amountof discussions (but not necessarily theirquality... ). It is impossible here to give afair survey of the very wide range of resultscovered in the poster sessions. We shall se-lect here only one area related to some cur-rent research interests of the organizers.Given the fact that the hosts of the meetingwithheld their work from the oral presenta-tions, following a good tradition to leavemore room for the lectures of the guests,this particular selection may perhaps seemsfair enough. After the discussions on 17thcentury science, 19th century science andearly 20th century science (i.e. quantumchemistry being based on the Schrödingerand Dirac equations of 1926–1929 or semi-classical theory being based on the evenearlier ‘old quantum theory’) this area of re-search from the posters leads into the late20th century and 21st century with elec-troweak theory and the standard model andbeyond.

The topic to be addressed here can besummarized under the relatively newlycoined term ‘electroweak quantum chem-istry’ [106][107]. It deals with the inclusionof the parity violating weak nuclear force inquantum chemical calculations, with theaim of properly treating the quantum dy-namics and spectroscopy of chiral mole-cules including parity violation as reviewedin [108][109]. About five posters dealt withthis intriguing topic, which led to consider-able discussions. Some of the work by now is available in print [68][87][88][106–108][110–112].

Fig. 34. Dominik Marx, Bochum, chairing thesession with Doltsinis and Parrinello

Fig. 35. Michele Parrinello, Lugano andZürich


Extracurricular Activities

The report would be incomplete with-out mentioning at least one of the extracur-ricular activities. Splendid weather onTuesday afternoon made the excursion tothe Stockhorn an exceptional event, withwide views over the Bernese alps. Severaloptions were available including one allbus and cable car option, but also quite ex-tensive and strenuous hiking, which someof the participants chose, while the largemajority put up with a combined hikingand cable car version. Fig. 36 shows thepicture of some part of the group (after re-covering from the excursion) and Fig. 37shows the mountain and lake theme of theconference logo which accompanied theexcursion.

AcknowledgmentParticular support was provided by the divi-

sion chemical research of the Swiss Chemical

Society. Further financial support came from theETH Zürich (SEP – Computational Sciences),the laboratory of Physical Chemistry of ETH,the Royal Society of Chemistry (for the PCCPlecture), from the Swiss National Science Foun-dation, and Swiss chemical industry, the KGF(see Fig. 38). Most of the photographs were tak-en by Sofia Deloudi, while the group photo wastaken by Marius Lewerenz, thanks to all of themfor their expert help and great work. For twominireviews see [113][114].

Received: April 8, 2004

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Fig. 38. Industry Sponsors


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Theoretical Chemistry: Molecular Spectroscopy and Dynamics