Evaluation of the importance of spin-orbit couplings in the nonadiabatic quantum dynamics with quantum fidelity and with its efficient “on-the-fly” ab initio semiclassical approximation
Year: 2012
Type: article
Abstract: We propose to measure the importance of spin-orbit couplings (SOCs) in the nonadiabatic molecular quantum dynamics rigorously with quantum fidelity. To make the criterion practical, quantum fidelity is estimated efficiently with the multiple-surface dephasing representation (MSDR). The MSDR is a semiclassical method that includes nuclear quantum effects through interference of mixed quantum-classical trajectories without the need for the Hessian of potential energy surfaces. Two variants of the MSDR are studied, in which the nuclei are propagated either with the fewest-switches surface hopping or with the locally mean field dynamics. The fidelity criterion and MSDR are first tested on one-dimensional model systems amenable to numerically exact quantum dynamics. Then, the MSDR is combined with "on-the-fly" computed electronic structure to measure the importance of SOCs and nonadiabatic couplings in the photoisomerization dynamics of CH(2)NH(2)(+) considering 20 electronic states and in the collision of F + H(2) considering six electronic states.
Source: The Journal of Chemical Physics
DOI: 10.1063/1.4738878
Authors: Tomáš Zimmermann, Jiří Vaníček
Institution: École Polytechnique Fédérale de Lausanne
Language: English
Subfield: Atomic and Molecular Physics, and Optics
Field: Physics and Astronomy
Domain: Physical Sciences
Open Access status: bronze
Award: G8440211138
OpenAlex ID: W2068801439