Quantifying charge resonance and multiexciton character in coupled chromophores by charge and spin cumulant analysis
- STC “Institute for Single Crystals,” National Academy of Sciences, Kharkov 61001 (Ukraine)
- Kimika Fakultatea, Euskal Herriko Unibertsitatea (UPV/EHU) and Donostia International Physics Center (DIPC), P.K. 1072, 20080 Donostia (Spain)
- Department of Chemistry, University of Southern California, Los Angeles, California 90089-0482 (United States)
We extend excited-state structural analysis to quantify the charge-resonance and multi-exciton character in wave functions of weakly interacting chromophores such as molecular dimers. The approach employs charge and spin cumulants which describe inter-fragment electronic correlations in molecular complexes. We introduce indexes corresponding to the weights of local, charge resonance, and biexciton (with different spin structure) configurations that can be computed for general wave functions thus allowing one to quantify the character of doubly excited states. The utility of the approach is illustrated by applications to several small dimers, e.g., He-H{sub 2}, (H{sub 2}){sub 2}, and (C{sub 2}H{sub 4}){sub 2}, using full and restricted configuration interaction schemes. In addition, we present calculations for several systems relevant to singlet fission, such as tetracene, 1,6-diphenyl-1,3,5-hexatriene, and 1,3-diphenylisobenzofuran dimers.
- OSTI ID:
- 22415961
- Journal Information:
- Journal of Chemical Physics, Vol. 142, Issue 22; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
Similar Records
Quantifying local exciton, charge resonance, and multiexciton character in correlated wave functions of multichromophoric systems
Photoprocesses in diphenylpolyenes. 2. Excited-state interactions with stable free radicals