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Title: Surface hopping investigation of the relaxation dynamics in radical cations

Ionization processes can lead to the formation of radical cations with population in several ionic states. In this study, we examine the dynamics of three radical cations starting from an excited ionic state using trajectory surface hopping dynamics in combination with multiconfigurational electronic structure methods. The efficiency of relaxation to the ground state is examined in an effort to understand better whether fragmentation of cations is likely to occur directly on excited states or after relaxation to the ground state. The results on cyclohexadiene, hexatriene, and uracil indicate that relaxation to the ground ionic state is very fast in these systems, while fragmentation before relaxation is rare. Ultrafast relaxation is facilitated by the close proximity of electronic states and the presence of two- and three-state conical intersections. Examining the properties of the systems in the Franck-Condon region can give some insight into the subsequent dynamics.
Authors:
;  [1] ;  [2]
  1. Department of Chemistry, Temple University, Philadelphia, Pennsylvania 19122 (United States)
  2. Department of Physics, Stony Brook University, Stony Brook, New York 11794 (United States)
Publication Date:
OSTI Identifier:
22493663
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 144; Journal Issue: 3; Other Information: (c) 2016 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CATIONS; EFFICIENCY; ELECTRONIC STRUCTURE; EXCITED STATES; FRAGMENTATION; FRANCK-CONDON PRINCIPLE; GROUND STATES; IONIZATION; RADICALS; RELAXATION; SURFACES; URACILS