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Title: Signatures of vibronic coupling in two-dimensional electronic-vibrational and vibrational-electronic spectroscopies

Two-Dimensional Electronic-Vibrational (2D EV) spectroscopy and Two-Dimensional Vibrational-Electronic (2D VE) spectroscopy are new coherent four-wave mixing spectroscopies that utilize both electronically resonant and vibrationally resonant field-matter interactions to elucidate couplings between electronic and vibrational degrees of freedom. Here, a system Hamiltonian is developed to lay a foundation for interpreting the 2D EV and 2D VE signals that arise from a vibronically coupled molecular system in the condensed phase. A molecular system consisting of one anharmonic vibration and two electronic states is modeled. Equilibrium displacement of the vibrational coordinate and vibrational frequency shifts upon excitation to the first electronic excited state are included in our Hamiltonian through linear and quadratic vibronic coupling terms. We explicitly consider the nuclear dependence of the electronic transition dipole moment and demonstrate that these spectroscopies are sensitive to non-Condon effects. A series of simulations of 2D EV and 2D VE spectra obtained by varying parameters of the system, system-bath, and interaction Hamiltonians demonstrate that one of the following conditions must be met to observe signals: (1) non-zero linear and/or quadratic vibronic coupling in the electronic excited state, (2) vibrational-coordinate dependence of the electronic transition dipole moment, or (3) electronic-state-dependent vibrational dephasing dynamics. We explore how thesemore » vibronic interactions are manifested in the positions, amplitudes, and line shapes of the peaks in 2D EV and 2D VE spectroscopies.« less
Authors:
ORCiD logo [1] ; ORCiD logo [1]
  1. Univ. of Washington, Seattle, WA (United States). Dept. of Chemistry
Publication Date:
Grant/Contract Number:
SC0012450; CHE 1565759; DGE-1256082
Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 147; Journal Issue: 9; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Research Org:
Univ. of Washington, Seattle, WA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF); Camille and Henry Dreyfus Foundation
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 74 ATOMIC AND MOLECULAR PHYSICS; quantum chemical dynamics; nanomaterials; four wave mixing spectroscopy; electron spectroscopy; selection rule; transition moment; adiabatic theorem; light harvesting complexes; multidimensional spectroscopy; vibrational spectra
OSTI Identifier:
1474041
Alternate Identifier(s):
OSTI ID: 1378125

Gaynor, James D., and Khalil, Munira. Signatures of vibronic coupling in two-dimensional electronic-vibrational and vibrational-electronic spectroscopies. United States: N. p., Web. doi:10.1063/1.4991745.
Gaynor, James D., & Khalil, Munira. Signatures of vibronic coupling in two-dimensional electronic-vibrational and vibrational-electronic spectroscopies. United States. doi:10.1063/1.4991745.
Gaynor, James D., and Khalil, Munira. 2017. "Signatures of vibronic coupling in two-dimensional electronic-vibrational and vibrational-electronic spectroscopies". United States. doi:10.1063/1.4991745. https://www.osti.gov/servlets/purl/1474041.
@article{osti_1474041,
title = {Signatures of vibronic coupling in two-dimensional electronic-vibrational and vibrational-electronic spectroscopies},
author = {Gaynor, James D. and Khalil, Munira},
abstractNote = {Two-Dimensional Electronic-Vibrational (2D EV) spectroscopy and Two-Dimensional Vibrational-Electronic (2D VE) spectroscopy are new coherent four-wave mixing spectroscopies that utilize both electronically resonant and vibrationally resonant field-matter interactions to elucidate couplings between electronic and vibrational degrees of freedom. Here, a system Hamiltonian is developed to lay a foundation for interpreting the 2D EV and 2D VE signals that arise from a vibronically coupled molecular system in the condensed phase. A molecular system consisting of one anharmonic vibration and two electronic states is modeled. Equilibrium displacement of the vibrational coordinate and vibrational frequency shifts upon excitation to the first electronic excited state are included in our Hamiltonian through linear and quadratic vibronic coupling terms. We explicitly consider the nuclear dependence of the electronic transition dipole moment and demonstrate that these spectroscopies are sensitive to non-Condon effects. A series of simulations of 2D EV and 2D VE spectra obtained by varying parameters of the system, system-bath, and interaction Hamiltonians demonstrate that one of the following conditions must be met to observe signals: (1) non-zero linear and/or quadratic vibronic coupling in the electronic excited state, (2) vibrational-coordinate dependence of the electronic transition dipole moment, or (3) electronic-state-dependent vibrational dephasing dynamics. We explore how these vibronic interactions are manifested in the positions, amplitudes, and line shapes of the peaks in 2D EV and 2D VE spectroscopies.},
doi = {10.1063/1.4991745},
journal = {Journal of Chemical Physics},
number = 9,
volume = 147,
place = {United States},
year = {2017},
month = {9}
}