Dynamics and spectroscopy of CH sub(2)OO excited electronic states

The excited states of the Criegee intermediate CH sub(2)OO are studied in molecular dynamics simulations using directly potentials from multi-reference perturbation theory (MR-PT2). The photoexcitation of the species is simulated, and trajectories are propagated in time on the excited state. Some of...

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Published inPhysical chemistry chemical physics : PCCP Vol. 18; no. 16; pp. 10941 - 10946
Main Authors Kalinowski, Jaroslaw, eman, Elizabeth S, Kapnas, Kara M, Murray, Craig, Raesaenen, Markku, Benny Gerber, R
Format Journal Article
LanguageEnglish
Published 01.04.2016
Subjects
Electron states
Excitation
Excitation spectra
Photoexcitation
Simulation
Spectroscopy
Trajectories
Vibration
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Summary:The excited states of the Criegee intermediate CH sub(2)OO are studied in molecular dynamics simulations using directly potentials from multi-reference perturbation theory (MR-PT2). The photoexcitation of the species is simulated, and trajectories are propagated in time on the excited state. Some of the photoexcitation events lead to direct fragmentation of the molecule, but other trajectories describe at least several vibrations in the excited state, that may terminate by relaxation to the ground electronic state. Limits on the role of non-adiabatic contributions to the process are estimated by two different simulations, one that forces surface-hopping at potential crossings, and another that ignores surface hopping altogether. The effect of non-adiabatic transitions is found to be small. Spectroscopic implications and consequences for the interpretation of experimental results are discussed.
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ISSN:1463-9076
1463-9084
DOI:10.1039/c6cp00807k