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Title: The effects of site asymmetry on near-degenerate state-to-state vibronic mixing in flexible bichromophores

Abstract

Laser-induced fluorescence excitation and dispersed fluorescence spectra of a model flexible bichromophore, 1,1-diphenylethane (DPE), have been recorded under jet-cooled conditions in the gas phase in the region near the first pair of near-degenerate excited states (S 1 and S 2). The S 1 and S 2 origin transitions have been identified at 37 397 and 37 510 cm –1, a splitting of 113 cm –1. This splitting is four times smaller than the excitonic splitting calculated by ab initio methods at the EOM-CCSD/cc-pVDZ level of theory (410 cm –1), which necessarily relies on the Born-Oppenheimer approximation. Dispersed fluorescence spectra provide a state-to-state picture of the vibronic coupling. Furthermore, these results are compared with the results of a multimode vibronic coupling model capable of treating chromophores in asymmetric environments.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [3]
  1. Purdue Univ., West Lafayette, IN (United States); College of William and Mary, Williamsburg, VA (United States)
  2. Purdue Univ., West Lafayette, IN (United States); Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  3. Purdue Univ., West Lafayette, IN (United States)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Laboratory Directed Research and Development (LDRD) Program
OSTI Identifier:
1570631
Alternate Identifier(s):
OSTI ID: 1567931
Report Number(s):
LA-UR-19-29710
Journal ID: ISSN 0021-9606
Grant/Contract Number:  
89233218CNA000001; FG02-96ER14656
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 151; Journal Issue: 8; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Inorganic and Physical Chemistry

Citation Formats

Kidwell, Nathanael M., Nebgen, Benjamin Tyler, Slipchenko, Lyudmila V., and Zwier, Timothy S. The effects of site asymmetry on near-degenerate state-to-state vibronic mixing in flexible bichromophores. United States: N. p., 2019. Web. doi:10.1063/1.5107423.
Kidwell, Nathanael M., Nebgen, Benjamin Tyler, Slipchenko, Lyudmila V., & Zwier, Timothy S. The effects of site asymmetry on near-degenerate state-to-state vibronic mixing in flexible bichromophores. United States. doi:10.1063/1.5107423.
Kidwell, Nathanael M., Nebgen, Benjamin Tyler, Slipchenko, Lyudmila V., and Zwier, Timothy S. Wed . "The effects of site asymmetry on near-degenerate state-to-state vibronic mixing in flexible bichromophores". United States. doi:10.1063/1.5107423.
@article{osti_1570631,
title = {The effects of site asymmetry on near-degenerate state-to-state vibronic mixing in flexible bichromophores},
author = {Kidwell, Nathanael M. and Nebgen, Benjamin Tyler and Slipchenko, Lyudmila V. and Zwier, Timothy S.},
abstractNote = {Laser-induced fluorescence excitation and dispersed fluorescence spectra of a model flexible bichromophore, 1,1-diphenylethane (DPE), have been recorded under jet-cooled conditions in the gas phase in the region near the first pair of near-degenerate excited states (S1 and S2). The S1 and S2 origin transitions have been identified at 37 397 and 37 510 cm–1, a splitting of 113 cm–1. This splitting is four times smaller than the excitonic splitting calculated by ab initio methods at the EOM-CCSD/cc-pVDZ level of theory (410 cm–1), which necessarily relies on the Born-Oppenheimer approximation. Dispersed fluorescence spectra provide a state-to-state picture of the vibronic coupling. Furthermore, these results are compared with the results of a multimode vibronic coupling model capable of treating chromophores in asymmetric environments.},
doi = {10.1063/1.5107423},
journal = {Journal of Chemical Physics},
number = 8,
volume = 151,
place = {United States},
year = {2019},
month = {8}
}

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