Improved potential energy surfaces of thioanisole and the effect of upper surface variations on the product distribution upon photodissociation

Research output: Contribution to journalArticlepeer-review

8 Scopus citations

Abstract

Electronically nonadiabatic photodissociation can be investigated in detail by experiments. This provides an opportunity to validate the current theory of electronically nonadiabatic processes, but is great challenge because the time scale of photodissociation processes can be long compared to the current capability for accurate direct dynamics simulations. To circumvent this difficulty, we have been using analytic diabatic potential energy matrices, such that the simulation time scale can be extended to the nanosecond region without neglecting the effects of external electron correlation. In previous work, we have developed full-dimensional three-state potential energy matrices for thioanisole photodissociation. In the current work, we extend this work in two main ways: (i) we improve the treatment of the initial torsional potential, and (ii) we shift the potential energy surfaces to investigate the quantitative effect on the dissociation lifetimes and product branching ratios of changing the energy and location of the S1–S2 conical intersection.

Original languageEnglish (US)
Pages (from-to)737-743
Number of pages7
JournalChemical Physics
Volume515
DOIs
StatePublished - Nov 14 2018

Bibliographical note

Funding Information:
The authors are grateful to Shaohong Li for additional help, to Hua Guo and Changjian Xie for additional analysis of the PESs, and to Michael Ashfold for stimulating discussions of the dynamics. This work was supported in part by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under award number DE-SC0015997.

Funding Information:
The authors are grateful to Shaohong Li for additional help, to Hua Guo and Changjian Xie for additional analysis of the PESs, and to Michael Ashfold for stimulating discussions of the dynamics. This work was supported in part by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under award number DE-SC0015997 .

Publisher Copyright:
© 2018 Elsevier B.V.

Copyright:
Copyright 2018 Elsevier B.V., All rights reserved.

Fingerprint Dive into the research topics of 'Improved potential energy surfaces of thioanisole and the effect of upper surface variations on the product distribution upon photodissociation'. Together they form a unique fingerprint.

Cite this