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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:
ORCiD logo [1] ;  [2]
  1. Universidad del PaĆ­s Vasco (UPV) Euskal Herriko Unibertsitatea (EHU), Donostia (Spain). Donostia International Physics Center; Basque Foundation for Science, Bilbao (Spain)
  2. Univ. of Southern California, Los Angeles, CA (United States). Dept. of Chemistry
Publication Date:
Grant/Contract Number:
FG02-05ER15685
Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 144; Journal Issue: 1; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Research Org:
Univ. of Southern California, Los Angeles, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR) (SC-21); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); Basque Government
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1468795
Alternate Identifier(s):
OSTI ID: 1234175

Casanova, David, and Krylov, Anna I. Quantifying local exciton, charge resonance, and multiexciton character in correlated wave functions of multichromophoric systems. United States: N. p., Web. doi:10.1063/1.4939222.
Casanova, David, & Krylov, Anna I. Quantifying local exciton, charge resonance, and multiexciton character in correlated wave functions of multichromophoric systems. United States. doi:10.1063/1.4939222.
Casanova, David, and Krylov, Anna I. 2016. "Quantifying local exciton, charge resonance, and multiexciton character in correlated wave functions of multichromophoric systems". United States. doi:10.1063/1.4939222. https://www.osti.gov/servlets/purl/1468795.
@article{osti_1468795,
title = {Quantifying local exciton, charge resonance, and multiexciton character in correlated wave functions of multichromophoric systems},
author = {Casanova, David and Krylov, Anna I.},
abstractNote = {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.},
doi = {10.1063/1.4939222},
journal = {Journal of Chemical Physics},
number = 1,
volume = 144,
place = {United States},
year = {2016},
month = {1}
}