Journal
JOURNAL OF PHYSICAL CHEMISTRY A
Volume 114, Issue 33, Pages 8764-8771Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jp101761d
Keywords
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Funding
- Extreme Scale Computing Initiative at Pacific Northwest National Laboratory
- Office of Biological and Environmental Research in the US Department of Energy
- US Department of Energy by the Battelle Memorial Institute [DE-AC06-76RLO-1830]
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The proper description of electron transfer (ET) processes in mixed-valence compounds poses a significant challenge for commonly used theoretical approaches. In this paper we analyze the 1(2)A(2) and 2(2)A(2) potential energy surfaces of the Spiro cation (5,5'(4H,4H')-spirobitcyclopenta[c]pyrrole]2,2',6,6'-tetrahydro cation) which is a frequently used model to study ET processes We compare and contrast the results obtained with three different methods multireference perturbation theory, equation-of-motion coupled cluster theory, time-dependent density functional theory. We demonstrate that the proper inclusion of dynamical correlation effects plays a crucial role in the description of an avoided crossing between potential energy surfaces. We also find that proper balancing of the ground- and excited-state correlation effects is especially challenging in the vicinity of the 1(2)A(2) and 2(2)A(2) avoided crossing region.
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