Abstract
Recent developments in two-dimensional (2D) THz-Raman and 2D Raman spectroscopies have created the possibility for quantitatively investigating the role of many dynamic and structural aspects of the molecular system. We explain the significant points for properly simulating 2D vibrational spectroscopic studies of intermolecular modes using the full molecular dynamics approach, in particular, regarding the system size, the treatment of the thermostat, and inclusion of an Ewald summation for the induced polarizability. Moreover, using the simulation results for water employing various polarization functions, we elucidate the roles of permanent and induced optical properties in determining the 2D profiles of the signal.
Highlights
Intermolecular vibrations of molecular liquids and biological material in the frequency range 0–700 cmÀ1 play an essential role in many chemical and biological processes, because they promote reactive dynamics via interactions through intramolecular modes and because they are active at room temperature
While almost all full molecular dynamics (MD) simulations for 2D Raman spectroscopy of CS2 have been carried out using the first model,49,53–55 here we examine the validity of results obtained using a more reliable potential that includes the Coulomb interactions
We elucidated the important points involved in full MD simulations of 2D Raman and THz-Raman spectroscopic approaches
Summary
Pulses. Because 2D THz-Raman utilizes the dipole moment, in addition to the polarizability, the applicability of this spectroscopy is different from that of 2D Raman spectroscopy. the information obtained from 2D Raman and 2D THz-Raman spectroscopies can be used in a complementary manner to investigate the fundamental nature of intermolecular interactions.. In 2D Raman and 2D THz-Raman spectroscopic approaches, the threebody nonlinear response function of the molecular polarizability and/or the dipole moment is measured to monitor molecular motion. Because the complex profiles of such 2D signals depend on many dynamic and structural aspects of the molecular system, full molecular dynamics (MD) simulations for the nonlinear response function play important roles in the design of 2D spectroscopy experiments and the analysis of their results, in regard to intermolecular vibrations.
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