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Theoretical Chemistry

Our central field of research is Theoretical and Computational Chemistry, in particular Quantum Chemistry. We focus on theoretical developments that extend the scope of computational methodology, especially for large molecules, and we apply theoretical methods to study specific chemical problems, mostly in close cooperation with experimental partners. The activities of the group cover a broad methodological spectrum:

  • ab initio methods
  • density functional theory
  • semiempirical methods
  • combined quantum mechanical/molecular mechanical methods

Recent applications from these areas address the rovibrational spectra of small molecules, catalytic reactions of transition metal compounds, excited-state dynamics, and enzymatic reactions. They thus range from accurate calculations on small molecules to the approximate modeling of very complex systems with thousands of atoms.

Walter Thiel

Prof. Dr. Walter Thiel

Vita Awards Publications Official Functions
since 2001
Honorary Professor, Universität Düsseldorf
since 1999
Director, Max-Planck-Institut für Kohlenforschung
1992–1999
Full Professor, Universität Zürich
1987
Visiting Professor, University of California at Berkeley
1983–1992
Associate Professor, Universität Wuppertal
1981
Habilitation, Universität Marburg
1973–1975
Postdoctoral fellow, University of Texas at Austin (M.J.S. Dewar)
1971–1973
Doctoral studies, Universität Marburg (A. Schweig)
1966–1971
Chemistry studies, Universität Marburg
1949
Born in Treysa/Germany
2012
Liebig Medal, German Chemical Society
2008
Member, Nordrhein-Westfälische Akademie der Wissenschaften
2007
Member, International Academy of Quantum Molecular Sciences
2007
Member, Deutsche Akademie der Naturforscher Leopoldina
2002
Schrödinger Medal, World Association of Theoretical Chemists
1988
Förderpreis, Alfried-Krupp Stiftung
1982
Heisenberg Fellowship, Deutsche Forschungsgemeinschaft
1975
Liebig Fellowship, Verband der Chemischen Industrie
since 2012
Member of the Board of Governors, German Chemical Society
since 2012
Editorial Advisory Board, Accounts of Chemical Research
since 2012
Editorial Advisory Board, ACS Catalysis
since 2011
President, World Association of Theoretical and Computational Chemists
2010
Chairman, Gordon Conference on Computational Chemistry
since 2009
Member of the International Advisory Board, State Key Laboratory of Physical Chemistry (PCOSS), Xiamen, China
since 2008
Associate Editor, WIRES: Computational Molecular Sciences
since 2006
Member of the Kuratorium, Angewandte Chemie
since 2006
Chairman, BAR Committee of the Max Planck Society
2006–2008
Managing Director, Max-Planck-Institut für Kohlenforschung
since 2004
Member of the Scientific Advisory Board, Lise-Meitner Minerva Center for Quantum Chemistry, Jerusalem/Haifa, Israel
2004–2007
Member, Ständiger Ausschuss der Bunsengesellschaft
2002–2008
Section Editor, Encyclopedia of Computational Chemistry
2001–2005
Chairman, Arbeitsgemeinschaft Theoretische Chemie
2000–2006
Member of the Steering Committee, Bavarian Supercomputer Center
2000–2008
Member of the Review Board, Deutsche Forschungsgemeinschaft
since 1998
Advisory Editor, Journal of Computational Chemistry
since 1997
Advisory Editor, Theoretical Chemistry Accounts
1990–1992
Speaker, DFG-Forschergruppe: Reaktive Moleküle
1986–1992
Member of the Board, Institut für Angewandte Informatik, Wuppertal
2012

(442) K. Meier, W. Thiel, and W. F. van Gunsteren, J. Comput. Chem. 33, 363-378 (2012).
On the Effect of a Variation of the Force Field, Spatial Boundary Condition and Size of the QM Region in QM/MM MD Simulations.

(441) E. W. Hernández-Rodríguez, E. Sanchez-Garcia, R. Crespo-Otero, A. L. Montero-Alejo, L. A. Montero, and W. Thiel, J. Phys. Chem. B 116, 1060-1076 (2012).
Understanding Rhodopsin Mutations Linked to the Retinitis Pigmentosa Disease: a QM/MM and DFT/MRCI Study.

(440) G. Cui, Z. Lan, and W. Thiel, J. Am. Chem Soc. 134, 1662-1672 (2012).
Intramolecular Hydrogen Bonding Plays a Crucial Role in the Photophysics and Photochemistry of the GFP Chromophore.

(439)    J. Cao, R. Bjornsson, M. Bühl, W. Thiel, and T. van Mourik, Chem. Eur. J. 18, 184-195 (2012).
Modelling Zwitterions in Solution: 3-Fluoro-γ-Aminobutyric Acid (3F-GABA).
 

2011

(438) J. Petǔskova, M. Patil, S. Holle, C. W. Lehmann, W. Thiel, and M. Alcarazo, J. Am. Chem. Soc. 133, 20758-20760 (2011).
Synthesis, Structure, and Reactivity of Carbene-Stabilized Phosphorus(III)-Centered Trications [L3P]3+.

(437) T. C. Ramalho, D. H. Pereira, and W. Thiel, J. Phys. Chem. A 115, 13504-13512 (2011).
Thermal and Solvent Effects on NMR Indirect Spin-Spin Coupling Constants of a Prototypical Chagas Disease Drug.

(436) D. Doron, D. T. Major, A. Kohen, W. Thiel, and X. Wu, J. Chem. Theory Comput. 7, 3420-3437 (2011).
Hybrid Quantum and Classical Simulations of the Dihydrofolate Reductase Catalyzed Hydride Transfer Reaction on an Accurate Semi-Empirical Potential Energy Surface.

(435) W. Thiel, Angew. Chem. 123, 9382-9384 (2011); Angew. Chem. Int. Ed. 50, 9216-9217 (2011).
Theoretical Chemistry—Quo Vadis?

(434) P. Meletis, M. Patil, W. Thiel, W. Frank, and M. Braun, Chem. Eur. J. 17, 11243-11249 (2011).
Enantioselective and Diastereoselective Tsuji-Trost Allylic Alkylation of Lactones: An Experimental and Computational Study.

(433) M. Korth and W. Thiel, J. Chem. Theory Comput. 7, 2929-2936 (2011).
Benchmarking Semiempirical Methods for Thermochemistry, Kinetics, and Non-convalent Interactions: OMx Methods are almost as Accurate and Robust as DFT-GGA Methods for Organic Molecules.

(432) B. Inés, M. Patil, J. Carreras, R. Goddard, W. Thiel, and M. Alcarazo, Angew. Chem. 123, 8550-8553 (2011); Angew. Chem. Int. Ed. 50, 8400-8403 (2011).
Synthesis, Structure, and Reactivity of a Dihydrido Borenium Cation.

(431) S. N. Yurchenko, R. J. Barber, J. Tennyson, W. Thiel, and P. Jensen, J. Mol. Spectrosc. 268, 123-129 (2011).
Towards Efficient Refinement of Molecular Potential Energy Surfaces: Ammonia as a Case Study.

(430) E. Fabiano, Z. Lan, Y. Lu, and Walter Thiel, in: Conical Intersections: Theory, Computation and Experiment, Eds. W. Domcke, D. R. Yarkony, and H. Köppel, World Scientific Publishing, Singapore, 2011; chap. 12, pp. 463-496.
Nonadiabatic Trajectory Calculations with Ab Initio and Semiempirical Methods.

(429) J. Breidung and W. Thiel, in: Handbook of High-Resolution Spectroscopies, Eds.M. Quack and F. Merkt, Wiley, Chicester, UK, 2011; vol. 1, pp. 389-404.
Prediction of Vibrational Spectra from Ab Initio Theory.

(428) A. Yachmenev, S. N. Yurchenko, T. Ribeyre, and W. Thiel, J. Chem. Phys. 135, 074302/1-13 (2011).
High-Level Ab Initio Potential Energy Surfaces and Vibrational Energies of H2CS.

(427) Y. Lu, Z. Lan, and W. Thiel, Angew. Chem. 123, 6996-6999 (2011); Angew. Chem. Int. Ed. 50, 6864-6867 (2011).
Hydrogen Bonding Regulates the Monomeric Nonradiative Decay of Adenine in DNA Strands.

(426) A. Kazaryan, Z. Lan, L. V. Schäfer, W. Thiel, and M. Filatov, J. Chem. Theory Comput. 7, 2189-2199 (2011).
Surface Hopping Excited-State Dynamics Study of the Photoisomerization of a Light-Driven Fluorene Molecular Rotary Motor.

(425) A. Metzelthin, E. Sánchez-Garcia, Ö. Birer, G. Schwaab, W. Thiel, W. Sander, and M. Havenith, ChemPhysChem 12, 2009-2017 (2011).
Acetylene Furan Trimer Formation at 0.37 K as a Model for Ultracold Aggregation of Non- and Weakly Polar Molecules.

(424) Z. Lan, Y. Lu, E. Fabiano, and W. Thiel, ChemPhysChem 12, 1989-1998 (2011).
QM/MM Nonadiabatic Decay Dynamics of 9H-Adenine in Aqueous Solution.

(423)    A. Yachmenev, S. N. Yurchenko, P. Jensen , and W. Thiel, J. Chem. Phys. 134, 244307/1-11 (2011).
A New “Spectroscopic” Potential Energy Surface for Formaldehyde in its Ground Electronic State.

(422) O. Weingart, Z. Lan, A. Koslowski, and W. Thiel, J. Phys. Chem. Lett. 2, 1506-1509 (2011).
Chiral Pathways and Periodic Decay in cis-Azobenzene Photodynamics.

(421) S. Metz and W. Thiel, Coord. Chem. Rev., 255, 1085-1103 (2011).
Theoretical Studies on the Reactivity of Molybdenum Enzymes.

(420) D. Kumar, W. Thiel, and S. P. de Visser, J. Am. Chem. Soc., 133, 3869-3882 (2011).
Quantum Mechanics/Molecular Mechanics Study on the Oxygen Activation Process in Cysteine Dioxygenase Enzymes.

(419) Y.-W. Hsiao and W. Thiel, J. Phys. Chem. B, 115, 2097-2106 (2011).
pB2 Intermediate of the Photoactive Yellow Protein: Structure and Excitation Energies.

(418) T. Benighaus and W. Thiel, J. Chem. Theory Comput. 7, 238-249 (2011). Long-Range Electrostatic Effects in QM/MM Studies of Enzymatic Reactions: Application of the Solvated Macromolecule Boundary Potential.

(417) D. Kumar, A. Altun, S. Shaik, and W. Thiel, Faraday Discuss. 148, 373-383 (2011).
Water as Biocatalyst in Cytochrome P450.

2010

(416) Y.-W. Hsiao, E. Sanchez-Garcia, M. Doerr, and W. Thiel, J. Phys. Chem. B 114, 15413-15423 (2010).
Quantum Refinement of Protein Structures: Implementation and Application to the Red Fluorescent Protein DsRed.M1.

(415) M. R. Silva-Junior, M. Schreiber, S. P. A. Sauer, and W. Thiel, J. Chem. Phys. 133, 174318/1-13 (2010).
Benchmarks of Electronically Excited States: Basis Set Effects on CASPT2 Results.

(414) A. Anoop, W. Thiel, and F. Neese, J. Chem. Theory Comput. 6, 3137-3144 (2010).
A Local Pair Natural Orbital Coupled Cluster Study of Rh Catalyzed Asymmetric Olefin Hydrogenation.

(413) M. K. Kesharwani, W. Thiel, and B. Ganguly, J. Phys. Chem. A 114, 10684-10693 (2010). Probing the Influence of Anomeric Effects on the Lithium Affinity in 1,3-Diaza Systems: A Computational Study.

(412) S. N. Yurchenko, M. Carvajal, A. Yachmenev, W. Thiel, and P. Jensen, J. Quant. Spect. Rad. Transf. 111, 2279-2290 (2010).
A Theoretical-Spectroscopy, Ab-Initio-Based Study of the Electronic Ground State of 121SbH3.

(411) A. Yachmenev, S. N. Yurchenko, P. Jensen, O. Baum, T. F. Giesen, and W. Thiel, Phys. Chem. Chem. Phys. 12, 8387-8397 (2010). Theoretical Rotation-Torsion Spectra of HSOH.

(410) M. R. Silva-Junior and W. Thiel, J. Chem. Theory Comput. 6, 1546-1564 (2010). Benchmark of Electronically Excited States for Semiempirical Methods: MNDO, AM1, PM3, OM1, OM2, OM3, INDO/S and INDO/S2.

(409) H. Bruns, M. Patil, J. Carreras, A. Vázquez, W. Thiel, R. Goddard, and M. Alcarazo, Angew. Chem. 122, 3762-3766 (2010); Angew. Chem. Int. Ed. 49, 3680-3683 (2010). Synthesis and Coordination Properties of Nitrogen (I)-Based Ligands.

(408) E. Sanchez-Garcia, M. Doerr, and W. Thiel, J. Comput. Chem. 31, 1603-1612 (2010). QM/MM Study of the Absorption Spectra of DsRed.M Chromophores.

(407) M. R. Silva-Junior, S. P. A. Sauer, M. Schreiber, and W. Thiel, Mol. Phys. 108, 453-465 (2010).
Basis Set Effects on Coupled Cluster Benchmarks of Electronically Ecxited States: CC3, CCSDR(3) and CC2.

(406) M. Alcarazo, T. Stork, A. Anoop, W. Thiel, and A. Fürstner, Angew. Chem. 122, 2596-2600 (2010); Angew. Chem. Int. Ed. 49, 2542-2546 (2010).
Steering the Surprising by Modul π-Acceptor Properties of N-Heterocyclic Carbenes: Implications for Gold Catalysis.

(405) A. Yachmenev, S. N. Yurchenko, I. Paidarova, P. Jensen, W. Thiel, and S. P. A. Sauer, J. Chem. Phys. 132, 114305/1-15 (2010). Thermal Averaging of the Indirect Nuclear Spin-Spin Coupling Constants of Ammonia: The Importance of the Large Amplitude Inversion Mode.

(404) M. Altarsha, T. Benighaus, D. Kumar, and W. Thiel, J. Biol. Inorg. Chem. 15, 361-372 (2010). Coupling and Uncoupling Mechanisms in the Methoxy-Threonine Mutant of Cytochrome P450cam: A QM/MM Study.

(403) Q. Sun, M. Doerr, Z. Li, S. C. Smith, and W. Thiel, Phys. Chem. Chem. Phys. 12, 2450-2458 (2010).
QM/MM Studies of the Structural and Energetic Properties of the Far-red Fluorescent Protein HcRed.

(402) S. Shaik, S. Cohen, Y. Wang, H. Chen, D. Kumar, and W. Thiel, Chem. Rev. 110, 949-1017 (2010).
P450 Enzymes: Their Structure, Reactivity and Selectivity, Modeled by QM/MM Calculations.

(401) S. Metz and W. Thiel, J. Phys. Chem. B 114, 1506-1517 (2010).
QM/MM Studies of Xanthine Oxidase: Variations of Cofactor, Substrate, and Active-Site Glu802.

(400) J. M. Dieterich, H.-J. Werner, R. A. Mata, S. Metz, and W. Thiel, J. Chem. Phys. 132, 035101/1-10 (2010).
Reductive Half-Reaction of Aldehyde Oxidoreductase toward Acetaldehyde: Ab Initio and Free Energy QM/MM Calculations.

(399) M. Parac, M. Doerr, C. M. Marian, and W. Thiel, J. Comput Chem. 31, 90-106 (2010).
QM/MM Calculation of Solvent Effects on Absorption Spectra of Guanine.

 

Research Topics

Ab initio Methods
Ab initio Methods

Ab initio Methods

We compute vibration-rotation spectra of small molecules with high accuracy using correlated ab initio methods with large basis sets. In our past research in this area, coupled cluster CCSD(T) calculations were combined with second-order rovibrational perturbation theory to predict the spectroscopic constants of small reactive molecules, with sufficient accuracy to guide their spectroscopic identification and to assist in the analysis of their high-resolution vibration-rotation spectra. More recently, we have developed and implemented a general variational treatment of nuclear motion that allows the prediction of rovibrational energies and intensities not only for semirigid molecules, but also for molecules with large amplitude motion and for high rotational excitation. The variational calculations are based on accurate ab initio potential energy surfaces and dipole moment surfaces obtained at the coupled cluster level. Recent applications include the computation of complete rovibrational line lists for ammonia, the explanation of the unexpected intensity anomalies observed for oxadisulfane (HSOH), and purely theoretical predictions for thioformaldehyde with wavenumber accuracy. In the realm of electronic spectroscopy, we use high-level ab initio methods to provide theoretical benchmark data for the electronically excited states of representative organic chromophores.

Density functional theory
Density functional theory

Density functional theory

We use density functional methods in studies of transition metal compounds to understand and predict their properties, with special emphasis on their electronic structure and catalytic reactivity. Much of the work on homogeneous catalysis involves a close collaboration with the experimental groups at our Institute and aims at a detailed mechanistic understanding of the reactions studied experimentally.

Such DFT applications include studies of:

* the mechanism of Ru-catalyzed olefin metathesis
* the stereochemistry of zirconocene-catalyzed olefin polymerization
* the activation of precatalysts in Pt- and Ru-catalyzed hydrosilylation
* the enantioselectivity of Rh-catalyzed hydrogenation
* the mechanism of Pd-catalyzed cross coupling reactions
* the origin of selectivity in Pd-catalyzed allylic alkylation reactions
* the electronic structure and spectra of iron-corrole complexes
* the electronic structure of carbon(0) and nitrogen(I) coordination compounds

DFT methods are also used as QM components in QM/MM investigations of enzymatic reactions.
 

Semiempirical methods
Semiempirical methods

Semiempirical methods

This long-term project aims at the development of improved semiempirical quantum-chemical methods that can be employed to study ever larger molecules with useful accuracy. This includes the development of more efficient algorithms and computer programs. Applications are usually motivated by requests from experimental partners or by topical chemical problems, but they also serve to explore the limits of new methods and codes.

Methodological activities include:

  • the incorporation of orthogonalization corrections at the NDDO level
  • the parameterization of the resulting OM approaches
  • the implementation of the GUGACI method in a semiempirical context
  • the implementation of semiempirical linear scaling techniques
  • the derivation and implementation of analytic derivatives
  • the use of genetic algorithms for semiempirical parameterizations
  • the implementation of surface hopping molecular dynamics

In the past, we have applied semiempirical MNDO-type methods extensively to study the properties of fullerenes. Our emphasis has now shifted towards the investigation of the photochemistry of large organic chromophores at the OM2/GUGACI level using both static calculations and surface hopping simulations. Target systems include the nucleobases in the gas phase, in aqueous solution, and in DNA oligomers as well as fluorescent proteins, molecular motors, photochemical switches, and retinal models. In addition, semiempirical methods are used in QM/MM molecular dynamics simulations of enzymatic reactions.

Combined quantum mechanical/molecular mechanical methods (QM/MM)
Combined quantum mechanical/molecular mechanical methods (QM/MM)

Combined quantum mechanical/molecular mechanical methods (QM/MM)

This research focuses on hybrid approaches for large systems where the active center is treated by an appropriate quantum mechanical method, and the environment by a classical force field. It involves considerable method and code development. The QM/MM approach allows a specific modeling of complex systems such that most of the computational effort is spent on the chemically important part. Current applications primarily address biocatalysis and aim at a better understanding of enzymatic reactions including the role of the protein environment.

Methodological advances include:

  • the definition of suitable QM/MM coupling schemes (embedding)
  • the use of accurate correlated ab initio methods as QM component
  • the use of polarizable Drude-type force fields as MM component
  • the development of special techniques for QM/MM geometry optimizations
  • the implementation of methods for QM/MM free-energy calculations
  • the development of three-layer QM/MM/continuum treatments
  • the extension of QM/MM methodology to electronically excited states
  • the implementation of QM/MM-based quantum refinement for X-ray analysis
  • the development of a modular QM/MM software environment (ChemShell)

While the QM/MM technology can be applied to many complex systems, we are most interested in enzymatic reactions. Recent investigations at different QM/MM levels address biocatalysis by heme enzymes (e.g., cytochrome P450), molybdopterin enzymes (e.g., xanthine oxidase), cystein proteases, fluorinases, lipases, chorismate mutase, p-hydroxybenzoate hydroxylase, and cyclohexanone monooxygenase. In addition, we also perform QM/MM studies on the spectroscopic properties of proteins, for examples on the Raman spectra of phycocyanin, the NMR spectra of vanadium-containing haloperoxidases, and the electronic spectra of fluorescent proteins. Surface hopping QM/MM simulations allow us to explore the excited-state dynamics of chromophores embedded in an environment.

 

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Organisations
Arbeitsgemeinschaft Theoretische Chemie
Computional Chemistry List
Deutsche Bunsengesellschaft
Deutsche Forschungsgemeinschaft
Gesellschaft Deutscher Chemiker
International Academy of Quantum Molecular Sciences
World Association of Theoretical and Computational Chemists

Software
ACCELRYS
ACES
ADF
ChemShell
Gaussian
MOLCAS
MOLPRO
Schrödinger
TURBOMOLE

Conferences
ACS Meetings
CCL Conference List
GDCh Tagungen

Symposium
International Symposium on Theoretical and Computational Chemistry
Festschrift: Journal of Physical Chemistry A 2009, 113 (43)

Projects
RUB Solvation Science