An accurate and efficient Ehrenfest dynamics approach for calculating linear and nonlinear electronic spectra

Atsango, Austin O.; Montoya-Castillo, Andrés; Markland, Thomas E.

doi:10.1063/5.0138671

An accurate and efficient Ehrenfest dynamics approach for calculating linear and nonlinear electronic spectra

Journal Article · Thu Feb 16 23:00:00 EST 2023 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/5.0138671· OSTI ID:2421469

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OSTI

Linear and nonlinear electronic spectra provide an important tool to probe the absorption and transfer of electronic energy. Here, we introduce a pure state Ehrenfest approach to obtain accurate linear and nonlinear spectra that is applicable to systems with large numbers of excited states and complex chemical environments. We achieve this by representing the initial conditions as sums of pure states and unfolding multi-time correlation functions into the Schrödinger picture. By doing this, we show that one can obtain significant improvements in accuracy over the previously used projected Ehrenfest approach and that these benefits are particularly pronounced in cases where the initial condition is a coherence between excited states. While such initial conditions do not arise when calculating linear electronic spectra, they play a vital role in capturing multidimensional spectroscopies. We demonstrate the performance of our method by showing that it is able to quantitatively capture the exact linear, 2D electronic spectroscopy, and pump–probe spectra for a Frenkel exciton model in slow bath regimes and is even able to reproduce the main spectral features in fast bath regimes.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of California, Merced, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: SC0020203

OSTI ID:: 2421469

Alternate ID(s):: OSTI ID: 1957698

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 7 Vol. 158; ISSN 0021-9606

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

Country of Publication:: United States

Language:: English

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