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

Abstract

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.

Authors:
 [1];  [1];  [1];  [2]; ORCiD logo [1]
  1. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
  2. IBN T. J. Watson Research Center, Yorktown Heights, NY (United States); Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1369323
Alternate Identifier(s):
OSTI ID: 1390304
Grant/Contract Number:
AC02-76SF00515
Resource Type:
Journal Article: Published Article
Journal Name:
Journal of Chemical Theory and Computation
Additional Journal Information:
Journal Volume: 13; Journal Issue: 8; Journal ID: ISSN 1549-9618
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Li, Xin, Parrish, Robert M., Liu, Fang, Kokkila Schumacher, Sara I. L., and Martinez, Todd J. An Ab Initio Exciton Model Including Charge-Transfer Excited States. United States: N. p., 2017. Web. doi:10.1021/acs.jctc.7b00171.
Li, Xin, Parrish, Robert M., Liu, Fang, Kokkila Schumacher, Sara I. L., & Martinez, Todd J. An Ab Initio Exciton Model Including Charge-Transfer Excited States. United States. doi:10.1021/acs.jctc.7b00171.
Li, Xin, Parrish, Robert M., Liu, Fang, Kokkila Schumacher, Sara I. L., and Martinez, Todd J. Thu . "An Ab Initio Exciton Model Including Charge-Transfer Excited States". United States. doi:10.1021/acs.jctc.7b00171.
@article{osti_1369323,
title = {An Ab Initio Exciton Model Including Charge-Transfer Excited States},
author = {Li, Xin and Parrish, Robert M. and Liu, Fang and Kokkila Schumacher, Sara I. L. and Martinez, Todd J.},
abstractNote = {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.},
doi = {10.1021/acs.jctc.7b00171},
journal = {Journal of Chemical Theory and Computation},
number = 8,
volume = 13,
place = {United States},
year = {Thu Jun 15 00:00:00 EDT 2017},
month = {Thu Jun 15 00:00:00 EDT 2017}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1021/acs.jctc.7b00171

Citation Metrics:
Cited by: 4 works
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