An Ab Initio Exciton Model Including Charge-Transfer Excited States

Li, Xin; Parrish, Robert M.; Liu, Fang; Kokkila Schumacher, Sara I. L.; Martínez, Todd J.

doi:10.1021/acs.jctc.7b00171

Title: An Ab Initio Exciton Model Including Charge-Transfer Excited States

Journal Article · Thu Jun 15 00:00:00 EDT 2017 · Journal of Chemical Theory and Computation

DOI:https://doi.org/10.1021/acs.jctc.7b00171· OSTI ID:1369323

Li, Xin ^[1]; Parrish, Robert M. ^[1]; Liu, Fang ^[1]; Kokkila Schumacher, Sara I. L. ^[1];

^[1]

Department of Chemistry and the PULSE Institute, Stanford University, Stanford, California 94305, United States, SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States

Here, the Frenkel exciton model is a useful tool for theoretical studies of multichromophore systems. We recently showed that the exciton model could be used to coarse-grain electronic structure in multichromophoric systems, focusing on singly excited exciton states. However, our previous implementation excluded charge-transfer excited states, which can play an important role in light-harvesting systems and near-infrared optoelectronic materials. Recent studies have also emphasized the significance of charge-transfer in singlet fission, which mediates the coupling between the locally excited states and the multiexcitonic states. In this work, we report on an ab initio exciton model that incorporates charge-transfer excited states and demonstrate that the model provides correct charge-transfer excitation energies and asymptotic behavior. Comparison with TDDFT and EOM-CC2 calculations shows that our exciton model is robust with respect to system size, screening parameter, and different density functionals. Inclusion of charge-transfer excited states makes the exciton model more useful for studies of singly excited states and provides a starting point for future construction of a model that also includes double-exciton states.

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Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1369323

Alternate ID(s):: OSTI ID: 1390304

Journal Information:: Journal of Chemical Theory and Computation, Journal Name: Journal of Chemical Theory and Computation; ISSN 1549-9618

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 78 works

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