Quantum dynamics simulations require prior knowledge of the potential energy surface as well as the kinetic energy operator. Typically, they are evaluated in a low-dimensional subspace of the full configuration space of the molecule as its dimensionality increases proportional to the number of atoms. This entails the challenge to find the most suitable subspace. We present an approach to design specially adapted reactive coordinates spanning this subspace. In addition to the essential geometric changes, these coordinates take into account the relaxation of the non-reactive coordinates without the necessity of performing geometry optimizations at each grid point. The method is demonstrated for an ultrafast photoinduced bond cleavage in a commonly used organic precursor for the generation of electrophiles. The potential energy surfaces for the reaction as well as the Wilson G-matrix as part of the kinetic energy operator are shown for a complex chemical reaction, both including the relaxation of the non-reactive coordinates on equal footing. A microscopic interpretation of the shape of the G-matrix elements allows to analyze the impact of the non-reactive coordinates on the kinetic energy operator. Additionally, we compare quantum dynamics simulations with and without the relaxation of the non-reactive coordinates included in the kinetic energy operator to demonstrate its influence.
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21 June 2016
Research Article|
June 17 2016
Design of specially adapted reactive coordinates to economically compute potential and kinetic energy operators including geometry relaxation
Sebastian Thallmair;
Sebastian Thallmair
1Department Chemie,
Ludwig-Maximilians-Universität München
, D-81377 München, Germany
2Lehrstuhl für BioMolekulare Optik,
Ludwig-Maximilians-Universität München
, D-80538 München, Germany
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Matthias K. Roos;
Matthias K. Roos
1Department Chemie,
Ludwig-Maximilians-Universität München
, D-81377 München, Germany
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Regina de Vivie-Riedle
Regina de Vivie-Riedle
a)
1Department Chemie,
Ludwig-Maximilians-Universität München
, D-81377 München, Germany
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a)
Electronic mail: regina.de_vivie@cup.uni-muenchen.de
J. Chem. Phys. 144, 234104 (2016)
Article history
Received:
March 15 2016
Accepted:
May 27 2016
Citation
Sebastian Thallmair, Matthias K. Roos, Regina de Vivie-Riedle; Design of specially adapted reactive coordinates to economically compute potential and kinetic energy operators including geometry relaxation. J. Chem. Phys. 21 June 2016; 144 (23): 234104. https://doi.org/10.1063/1.4953667
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