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EOMCC, MRPT, and TDDFT Studies of Charge Transfer Processes in Mixed-Valence Compounds: Application to the Spiro Molecule†

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William R. Wiley Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99352 USA, and Fundamental and Computational Sciences Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99352 USA
Part of the “Klaus Ruedenberg Festschrift”.
To whom correspondence should be addressed. E-mail: [email protected]
Environmental Molecular Sciences Laboratory
Fundamental and Computational Sciences Directorate
Cite this: J. Phys. Chem. A 2010, 114, 33, 8764–8771
Publication Date (Web):June 11, 2010
https://doi.org/10.1021/jp101761d
Copyright © 2010 American Chemical Society
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    Abstract

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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 12A2 and 22A2 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 12A2 and 22A2 avoided crossing region.

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