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

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4939842· OSTI ID:1435412
 [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)
+ Show Author Affiliations

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.

Research Organization:
Temple Univ., Philadelphia, PA (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
FG02-08ER15983; FG02-08ER15984
OSTI ID:
1435412
Alternate ID(s):
OSTI ID: 1235097
Journal Information:
Journal of Chemical Physics, Vol. 144, Issue 3; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 28 works
Citation information provided by
Web of Science

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Cited By (3)

Computing the Ultrafast and Radiationless Electronic Excited State Decay of Cytosine and 5‐methyl‐cytosine Cations: Uncovering the Role of Dynamic Electron Correlation journal May 2019
Calculations of non-adiabatic couplings within equation-of-motion coupled-cluster framework: Theory, implementation, and validation against multi-reference methods journal January 2018
Ultraviolet relaxation dynamics in uracil: Time-resolved photoion yield studies using a laser-based thermal desorption source journal July 2018

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Ionizaiton
Isomerization
Non adiabatic reactions
Excited states
Non adiabatic couplings
Dissociation
Normal modes
Ground states
Surface dynamics