期刊
JOURNAL OF CHEMICAL PHYSICS
卷 153, 期 4, 页码 -出版社
AMER INST PHYSICS
DOI: 10.1063/5.0013739
关键词
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资金
- Department of Energy Basic Energy Sciences CTC program [DE-SC0019053]
- Department of Energy Basic Energy Sciences CPIMS program [DE-SC0019053]
- National Science Foundation Major Research Instrumentation program [ACI-1429783]
- U.S. Department of Energy (DOE) [DE-SC0019053] Funding Source: U.S. Department of Energy (DOE)
First-principles modeling of nonlinear optical spectra in the condensed phase is highly challenging because both environment and vibronic interactions can play a large role in determining spectral shapes and excited state dynamics. Here, we compute two dimensional electronic spectroscopy (2DES) signals based on a cumulant expansion of the energy gap fluctuation operator, with specific focus on analyzing mode mixing effects introduced by the Duschinsky rotation and the role of the third order term in the cumulant expansion for both model and realistic condensed phase systems. We show that for a harmonic model system, the third order cumulant correction captures effects introduced by a mismatch in curvatures of ground and excited state potential energy surfaces, as well as effects of mode mixing. We also demonstrate that 2DES signals can be accurately reconstructed from purely classical correlation functions using quantum correction factors. We then compute nonlinear optical spectra for the Nile red and methylene blue chromophores in solution, assessing the third order cumulant contribution for realistic systems. We show that the third order cumulant correction is strongly dependent on the treatment of the solvent environment, revealing the interplay between environmental polarization and the electronic-vibrational coupling.
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