In this study, we use a multimode Brownian oscillator model and four-body correlation functions to calculate third-order two-dimensional (2D) infrared spectra and fifth-order 2D IR-IR-Raman-Raman spectra to investigate the intermolecular and intramolecular anharmonic coupling of bulk water. By considering the nonlinearity of system-bath interactions and solving discretized hierarchical equations of motion in mixed Liouville-Wigner space, we obtain both linear and nonlinear spectra in a non-Markovian and nonperturbative regime. The calculated 2D spectra for different modes reveal detailed information about the mode-mode interactions under thermal relaxation and dephasing at finite temperature.
To investigate the possibility of measuring the intermolecular and intramolecular anharmonic coupling of balk water, we calculate third-order two-dimensional (2D) infrared spectra and fifth-order 2D IR-IR-Raman-Raman spectra expressed in terms of four-body correlation functions of optical observables. For this purpose, a multimode Brownian oscillator model of four interacting anharmonic oscillators strongly coupled to their respective heat baths is employed. The nonlinearity of system-bath interactions is considered to describe thermal relaxation and vibrational dephasing. The linear and nonlinear spectra are then computed in a non-Markovian and nonperturbative regime in a rigorous manner using discretized hierarchical equations of motion in mixed Liouville-Wigner space. The calculated 2D spectra for stretching-bending, bending-librational, stretching-librational, and stretching-translational modes consist of various positive and negative peaks exhibiting essential details of intermolecular and intramolecular mode-mode interactions under thermal relaxation and dephasing at finite temperature. (c) 2023 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license(http://creativecommons.org/licenses/by/4.0/)
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