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American Institute of Physics, The Journal of Chemical Physics, 1(144), p. 014102

DOI: 10.1063/1.4939222

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Quantifying local exciton, charge resonance, and multiexciton character in correlated wave functions of multichromophoric systems

Journal article published in 2016 by David Casanova ORCID, Anna I. Krylov
This paper is made freely available by the publisher.
This paper is made freely available by the publisher.

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Abstract

A new method for quantifying the contributions of local excitation, charge resonance, and multiexciton configurations in correlated wave functions of multichromophoric systems is presented. The approach relies on fragment-localized orbitals and employs spin correlators. Its utility is illustrated by calculations on model clusters of hydrogen, ethylene, and tetracene molecules using adiabatic restricted-active-space configuration interactionwave functions. In addition to the wave function analysis, this approach provides a basis for a simple state-specific energy correction accounting for insufficient description of electron correlation. The decomposition scheme also allows one to compute energies of the diabatic states of the local excitonic, charge-resonance, and multi-excitonic character. The new method provides insight into electronic structure of multichromophoric systems and delivers valuable reference data for validating excitonic models.