Vibrationally resolved photoelectron spectroscopy of oligothiophene radical anions

Thurston, Glen K.; Sagan, Cole R.; Garand, Etienne

doi:10.1063/1.5124925

Vibrationally resolved photoelectron spectroscopy of oligothiophene radical anions

Journal Article · Mon Oct 28 00:00:00 EDT 2019 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.5124925· OSTI ID:1593861

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Univ. of Wisconsin, Madison, WI (United States); University of Wisconsin-Madison Department of Chemistry
Univ. of Wisconsin, Madison, WI (United States)

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.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Wisconsin, Madison, WI (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0010326

OSTI ID:: 1593861

Alternate ID(s):: OSTI ID: 1571344

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 16 Vol. 151; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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