Journal
JOURNAL OF CHEMICAL PHYSICS
Volume 147, Issue 9, Pages -Publisher
AMER INST PHYSICS
DOI: 10.1063/1.4991745
Keywords
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Funding
- U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences [DE-SC0012450]
- National Science Foundation [CHE 1565759]
- NSF GRFP, Division of Graduate Education [DGE-1256082]
- Camille and Henry Dreyfus Foundation
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1565759] Funding Source: National Science Foundation
- U.S. Department of Energy (DOE) [DE-SC0012450] Funding Source: U.S. Department of Energy (DOE)
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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. A system Hamiltonian is developed here 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. Published by AIP Publishing.
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