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Title: Interfacing the Ab initio multiple spawning method with electronic structure methods in GAMESS: Photodecay of trans-Azomethane

Journal Article · · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
DOI:https://doi.org/10.1021/jp508242j· OSTI ID:1233235
 [1];  [2];  [3];  [4];  [1]
  1. Ames Laboratory (AMES), Ames, IA (United States); Iowa State Univ., Ames, IA (United States)
  2. Univ. of Pittsburgh, Pittsburgh, PA (United States)
  3. Univ. of Nevada, Reno, NV (United States)
  4. Stanford Univ., Stanford, CA (United States)
+ Show Author Affiliations

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 ~60–200 fs. As a result, these short lifetimes are in agreement with time-resolved photoionization mass spectroscopy experiments.

Research Organization:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
AC02-07CH11358
OSTI ID:
1233235
Report Number(s):
IS-J-8543
Journal Information:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Vol. 118, Issue 46; ISSN 1089-5639
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 30 works
Citation information provided by
Web of Science

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  • Cattaneo, Paola; Persico, Maurizio
  • Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta), Vol. 103, Issue 5 https://doi.org/10.1007/s002149900045
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Cited By (4)

Nonadiabatic transition state theory: Application to intersystem crossings in the active sites of metal-sulfur proteins journal March 2016
Quantum mechanical/molecular mechanical trajectory surface hopping molecular dynamics simulation by spin-flip time-dependent density functional theory journal January 2020
Theoretical investigations of spin‐orbit coupling and intersystem crossing in reaction carbon dioxide activated by [Re(CO) 2 ] + journal November 2019
Trajectory surface hopping molecular dynamics simulation by spin-flip time-dependent density functional theory journal May 2019

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