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

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

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.

Publication types

  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Electrons
  • Molecular Dynamics Simulation*
  • Quantum Theory*
  • Spiro Compounds / chemistry*

Substances

  • Spiro Compounds