Vibrationally resolved photoelectron spectroscopy of oligothiophene radical anions
Abstract
Vibrationally resolved photoelectron spectroscopy of terthiophene, quaterthiophene, and quinquethiophene radical anions is presented. The increased spectral resolution afforded by the combination of slow photoelectron velocity-map imaging and ion cooling in a cryogenic ion trap allows the characterization of vibronic structures within the S0 and T1 states. Analysis of the spectra, aided by electronic structure calculations and Franck-Condon simulations, revealed evidence for significant contributions from kinetically trapped higher energy conformers in the anion-to-triplet transitions. Unlike the lowest energy structures, where all the thiophene linkers are in the trans configuration, these higher energy conformers contain at least one cis linker. We also found that the adiabatic Franck-Condon simulations drastically underestimated the intensities of some vibronic features in the singlet ground state spectra due to large geometry changes upon photodetachment and anharmonic couplings in the singlet state.
- Authors:
-
- Univ. of Wisconsin, Madison, WI (United States)
- Publication Date:
- Research Org.:
- Univ. of Wisconsin, Madison, WI (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1593861
- Alternate Identifier(s):
- OSTI ID: 1571344
- Grant/Contract Number:
- SC0010326
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Chemical Physics
- Additional Journal Information:
- Journal Volume: 151; Journal Issue: 16; 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
Citation Formats
Thurston, Glen K., Sagan, Cole R., and Garand, Etienne. Vibrationally resolved photoelectron spectroscopy of oligothiophene radical anions. United States: N. p., 2019.
Web. doi:10.1063/1.5124925.
Thurston, Glen K., Sagan, Cole R., & Garand, Etienne. Vibrationally resolved photoelectron spectroscopy of oligothiophene radical anions. United States. https://doi.org/10.1063/1.5124925
Thurston, Glen K., Sagan, Cole R., and Garand, Etienne. Mon .
"Vibrationally resolved photoelectron spectroscopy of oligothiophene radical anions". United States. https://doi.org/10.1063/1.5124925. https://www.osti.gov/servlets/purl/1593861.
@article{osti_1593861,
title = {Vibrationally resolved photoelectron spectroscopy of oligothiophene radical anions},
author = {Thurston, Glen K. and Sagan, Cole R. and Garand, Etienne},
abstractNote = {Vibrationally resolved photoelectron spectroscopy of terthiophene, quaterthiophene, and quinquethiophene radical anions is presented. The increased spectral resolution afforded by the combination of slow photoelectron velocity-map imaging and ion cooling in a cryogenic ion trap allows the characterization of vibronic structures within the S0 and T1 states. Analysis of the spectra, aided by electronic structure calculations and Franck-Condon simulations, revealed evidence for significant contributions from kinetically trapped higher energy conformers in the anion-to-triplet transitions. Unlike the lowest energy structures, where all the thiophene linkers are in the trans configuration, these higher energy conformers contain at least one cis linker. We also found that the adiabatic Franck-Condon simulations drastically underestimated the intensities of some vibronic features in the singlet ground state spectra due to large geometry changes upon photodetachment and anharmonic couplings in the singlet state.},
doi = {10.1063/1.5124925},
journal = {Journal of Chemical Physics},
number = 16,
volume = 151,
place = {United States},
year = {Mon Oct 28 00:00:00 EDT 2019},
month = {Mon Oct 28 00:00:00 EDT 2019}
}
Web of Science
Figures / Tables:
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