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Interfacing the Ab Initio Multiple Spawning Method with Electronic Structure Methods in GAMESS: Photodecay of trans-Azonnethane

TitleInterfacing the Ab Initio Multiple Spawning Method with Electronic Structure Methods in GAMESS: Photodecay of trans-Azonnethane
Publication TypeJournal Article
Year of Publication2014
AuthorsGaenko, A, DeFusco, A, Varganov, SA, Martinez, TJ, Gordon, MS
JournalJournal of Physical Chemistry A
Volume118
Pagination10902-10908
Date Published11
Type of ArticleArticle
ISBN Number1089-5639
Accession NumberWOS:000345474500004
Keywordsazomethane, conical intersections, energy, excited-state dynamics, fuels, gaussian wavepackets, nonadiabatic dynamics, photochemistry, photodissociation, quantum molecular-dynamics, resolved photoelectron-spectroscopy, solar
Abstract

This work presents a nonadiabatic molecular dynamics study of the nonradiative decay of photoexcited trans-azomethane, using the ab initio multiple spawning (AIMS) program that has been interfaced with the General Atomic and Molecular Electronic Structure System (GAMESS) quantum chemistry package for on-the-fly electronic structure evaluation. The interface strategy is discussed, and the capabilities of the combined programs are demonstrated with a nonadiabatic molecular dynamics study of the nonradiative decay of photoexcited trans-azomethane. Energies, gradients, and nonadiabatic coupling matrix elements were obtained with the state-averaged complete active space self-consistent field method, as implemented in GAMESS. The influence of initial vibrational excitation on the outcome of the photoinduced isomerization is explored. Increased vibrational excitation in the CNNC torsional mode shortens the excited state lifetime. Depending on the degree of vibrational excitation, the excited state lifetime varies from similar to 60200 fs. These short lifetimes are in agreement with time-resolved photoionization mass spectroscopy experiments.

DOI10.1021/jp508242j
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