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J Chem Theory Comput. 2012 Aug 14;8(8):2661-8. doi: 10.1021/ct300318g. Epub 2012 Jul 6.

Calculating Off-Site Excitations in Symmetric Donor-Acceptor Systems via Time-Dependent Density Functional Theory with Range-Separated Density Functionals.

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1
Department of Chemistry, University of Michigan , Ann Arbor, Michigan, United States.

Abstract

Time-dependent density functional theory with range-separated hybrid functionals is used to calculate off-site excitations involving transitions between spatially separated orbitals in weakly coupled systems. Although such off-site excitations involve charge transfer, orbital degeneracy in symmetrical systems results in linear combinations of off-site excitations with equal weights and therefore zero net charge-transfer character. Like other types of off-site excitations, such "hidden" charge-transfer excitations are not accurately captured by conventional density functionals. We show that the recently introduced Baer-Neuhauser-Livshitz range-separated hybrid functional accurately characterizes such hidden off-site excitation energies via applications to the ethene dimer model system and to dye-functionalized silsesquioxanes.

PMID:
26592111
DOI:
10.1021/ct300318g

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