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    J Phys Chem A. 2010 Aug 26;114(33):8764-71. doi: 10.1021/jp101761d.

    EOMCC, MRPT, and TDDFT studies of charge transfer processes in mixed-valence compounds: application to the spiro molecule.

    Source

    William R. Wiley Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99352 USA.

    Abstract

    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')-spirobi[cyclopenta[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.

    PMID:
    20540550
    [PubMed - indexed for MEDLINE]

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