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On the Importance of Initial Conditions for Excited-State Dynamics

Suchan, Jiří; Hollas, Daniel; Curchod, Basile F.E.; Slavicek, Petr

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Authors

Jiří Suchan

Daniel Hollas

Petr Slavicek



Abstract

Photodynamical simulations are increasingly used for exploring photochemical mechanisms and interpreting laser experiments. The vast majority of ab initio excited-state simulations are performed within semiclassical, trajectory-based approaches. Apart from the underlying electronic-structure theory, the reliability of the simulations is controlled by a selection of initial conditions for the classical trajectories. We discuss appropriate choices of initial conditions for simulations of different experimental arrangements: dynamics initiated by continuum-wave (CW) laser fields or triggered by ultrashort laser pulses. We introduce a new technique, CW-sampling, to treat the former case, based on the ideas of importance sampling, combined with the quantum thermostat approach based on the Generalized Langevin Equation (GLE) that allows for an efficient sampling of both position and momentum space. The CW-sampling is particularly important for photodynamical processes initiated by absorption at the tail of the UV absorption spectrum. We also emphasize the importance of non-Condon effects for the dynamics. We demonstrate the performance of our approach on the photodissociation of the CF2Cl2 molecule (freon CFC-12). A quantitative agreement with the experimental data is achieved with the use of empirical correlation energy correction (CEC) factor on top of FOMO-CASCI potential energy surfaces.

Citation

Suchan, J., Hollas, D., Curchod, B. F., & Slavicek, P. (2018). On the Importance of Initial Conditions for Excited-State Dynamics. Faraday Discussions, 212, 307-330. https://doi.org/10.1039/c8fd00088c

Journal Article Type Article
Acceptance Date May 25, 2018
Online Publication Date May 25, 2018
Publication Date Dec 1, 2018
Deposit Date May 25, 2018
Publicly Available Date Mar 29, 2024
Journal Faraday Discussions
Print ISSN 1359-6640
Electronic ISSN 1364-5498
Publisher Royal Society of Chemistry
Peer Reviewed Peer Reviewed
Volume 212
Pages 307-330
DOI https://doi.org/10.1039/c8fd00088c

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