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This paper investigates the intramolecular vibrational dynamics of liquid H2O and D2O using two-dimensional infrared spectroscopy simulations. The authors employ a hierarchical equations of motion (HEOM) approach to accurately model the non-Markovian and non-perturbative interactions between intramolecular modes and their thermal environment. By comparing the 2D spectra of H2O and D2O, the study reveals insights into the complex energy and phase relaxation dynamics influenced by anharmonic mode-mode coupling.
Isotopic substitution in water reveals intricate details of vibrational energy transfer and dephasing, offering a new lens into the interplay between intramolecular modes and their thermal environment.
We model, simulate, and analyze the intramolecular modes of liquid H2O and D2O to elucidate how energy excitation, relaxation, and vibrational dephasing interplay through anharmonic mode-mode coupling. Our analysis employs two-dimensional (2D) correlation spectra, a representative observable in nonlinear infrared vibrational spectroscopy. Accurate reproduction of these 2D spectral profiles requires not only a precise dynamical description of intramolecular vibrations but also an appropriate treatment of thermal environmental effects arising from strong interactions with surrounding molecules, which act as thermal baths. Capturing the essential features of the 2D spectra further demands a non-Markovian, non-perturbative, and nonlinear description of the interactions between intramolecular modes and their baths. To this end, we adopt a hierarchical equations of motion (HEOM) framework to compute the 2D spectra. By comparing the resulting spectra of H2O and D2O, we explore the underlying mechanisms governing their complex energy and phase relaxation dynamics.
