Full molecular dynamics simulations of molecular liquids for single-beam spectrally controlled two-dimensional Raman...

Single-beam spectrally controlled (SBSC) two-dimensional (2D) Raman spectroscopy is a unique 2D vibrational measurement technique utilizing trains of short pulses that are generated from a single broadband pulse by pulse shaping. This approach overcomes the difficulty of 2D Raman spectroscopy in dealing with small-signal extraction and avoids complicated low-order cascading effects, thus providing a new possibility for measuring the intramolecular and intermolecular modes of molecular liquids using fifth-order 2D Raman spectroscopy. Recently, for quantitatively investigating the mode-mode coupling mechanism, Hurwitz et al. [Opt. Express 28, 3803 (2020)] have developed a new pulse design for this measurement to separate the contributions of the fifth- and third-order polarizations, which are often overlapped in the original single-beam measurements. Here, we describe a method for simulating these original measurements and the new 2D Raman measurements on the basis of a second-order response function approach. We carry out full molecular dynamics simulations for carbon tetrachloride and liquid water using an equilibrium-nonequilibrium hybrid algorithm, with the aim of explaining the key features of the SBSC 2D Raman spectroscopic method from a theoretical point of view. The predicted signal profiles and intensities provide valuable information that can be applied to 2D spectroscopy experiments, allowing them to be carried out more efficiently.