Quantum Dynamics of a Photochemical Bond Cleavage Influenced by the Solvent Environment: A Dynamic Continuum Approach.
In every day chemistry, solvents are used to influence the outcome of chemical synthesis. Electrostatic effects stabilize polar configurations during the reaction and in addition dynamic solvent effects can emerge. How the dynamic effects intervene on the ultrafast time scale is in the focus of this theoretical study. We selected the photoinduced bond cleavage of Ph2CH-PPh3(+) for which the electrostatic interactions are negligible. Elaborate ultrafast pump-probe studies already exist and serve as a reference. We compared quantum dynamical simulations with and without environment and noticed the necessity to model the influence of the solvent cage on the reactive motions of the solute. The frictional force induced by the dynamic viscosity of the solvent is implemented in the quantum mechanical formalism with a newly developed approach called the dynamic continuum ansatz. Only when the environment is included are the experimentally observed products reproduced on the subpicosecond time scale.
†Department Chemie, Ludwig-Maximilians-Universität München, D-81377 München, Germany.|‡Lehrstuhl für BioMolekulare Optik, Ludwig-Maximilians-Universität München, D-80538 München, Germany.
Sebastian
S
Thallmair
†Department Chemie, Ludwig-Maximilians-Universität München, D-81377 München, Germany.
Markus
M
Kowalewski
†Department Chemie, Ludwig-Maximilians-Universität München, D-81377 München, Germany.
Julius P P
JP
Zauleck
†Department Chemie, Ludwig-Maximilians-Universität München, D-81377 München, Germany.
Matthias K
MK
Roos
†Department Chemie, Ludwig-Maximilians-Universität München, D-81377 München, Germany.
Regina
R
de Vivie-Riedle
ONIOM potential energy surfaces; conical intersection; dynamic solvent effects; heterolytic and homolytic bond cleavage; quantum dynamics