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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. Furthermore, examining the properties of the systems in the Franck-Condon region can give some insight into the subsequent dynamics.
Authors:
 [1] ;  [2] ;  [3]
  1. Temple Univ., Philadelphia, PA (United States); Univ. of Birmingham, Birmingham (United Kingdom)
  2. Stony Brook Univ., Stony Brook, NY (United States)
  3. Temple Univ., Philadelphia, PA (United States)
Publication Date:
Grant/Contract Number:
FG02-08ER15983; FG02-08ER15984
Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 144; Journal Issue: 3; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Research Org:
Temple Univ., Philadelphia, PA (United States)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Ionizaiton; Isomerization; Non adiabatic reactions; Excited states; Non adiabatic couplings; Dissociation; Normal modes; Ground states; Surface dynamics
OSTI Identifier:
1435412
Alternate Identifier(s):
OSTI ID: 1235097