Full-dimensional multi-state simulation of the photodissociation of thioanisole

Shaohong L. Li, Donald G. Truhlar

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8 Scopus citations

Abstract

The photodissociation of thioanisole is very interesting because the experiments of Lim and Kim provide evidence for mode-specific effects on the product distribution. They showed that, with a specific S-CH3 stretching mode being excited as the reagent is excited to the S1 electronic state, there is a sharp increase in the proportion of the ground-state product to the excited-state product. In the present work, we report 78 011 full-dimensional semiclassical multi-state trajectories of the photodissociation process using the coherent switching with decay of mixing dynamics method. The potential surfaces and couplings are based on electronic structure calculations that include dynamic correlation through second order perturbation theory. We report results for four sets of initial conditions, one corresponding roughly to 0-0 excitation and three corresponding to exciting one vibrational mode, to look for mode-specific effects. The simulations show no significant mode-specific effect on the product energy distributions, but they do show an effect on the distribution of minimum-energy gaps in the trajectories and on the lifetime for dissociation. In particular, excitation of the S-CH3 stretching mode leads to trajectories passing closer to the S1-S2 conical intersection and to shorter lifetimes. This provides a possible explanation of why experimental results are different for excitation of this vibration.

Original languageEnglish (US)
Article number044311
JournalJournal of Chemical Physics
Volume147
Issue number4
DOIs
StatePublished - Jul 28 2017

Bibliographical note

Funding Information:
This work was supported in part by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award No. DE-SC0015997. S.L.L. was also supported by a Doctoral Dissertation Fellowship at the University of Minnesota. Computational resources were provided by the University of Minnesota Supercomputing Institute and by the DOE Office of Science User Facilities at Molecular Science Computing Facility in the William R. Wiley Environmental Molecular Sciences Laboratory of Pacific Northwest National Laboratory and at the National Energy Research Scientific Computing Center (Contract No. DE-AC02-05CH11231).

Publisher Copyright:
© 2017 Author(s).

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