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

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 interaction wave 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.
Authors:
 [1] ;  [2] ;  [3]
  1. Kimika Fakultatea, Euskal Herriko Unibersitatea (UPV/EHU) and Donostia International Physics Center (DIPC), P.K. 1072, 20018 Donostia (Spain)
  2. (Spain)
  3. Department of Chemistry, University of Southern California, Los Angeles, California 90089-0482 (United States)
Publication Date:
OSTI Identifier:
22493611
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 144; Journal Issue: 1; Other Information: (c) 2016 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CONFIGURATION INTERACTION; CORRECTIONS; DECOMPOSITION; ELECTRON CORRELATION; ELECTRONIC STRUCTURE; ETHYLENE; EXCITATION; EXCITONS; HYDROGEN; MOLECULAR CLUSTERS; MOLECULES; RESONANCE; SPIN; TETRACENE; WAVE FUNCTIONS