Hydroxyl stretching vibrational mode is an important spectroscopic marker of structure and dynamics of water's hydrogen-bonding network. The complex interplay between intra- and intermolecular couplings results in significant delocalization of OH stretching vibrations and broadening of the OH-stretching band in IR and Raman spectra of liquid water. In order to disentangle the effects of inter- and intramolecular couplings on vibrational spectra of water, and quantify the role of intermolecular couplings on water's OH stretching band, Raman multivariate curve resolution spectra (MCR) were obtained recently from pure and isotopically dilute water. Further progress in interpreting experimental results requires theoretical approaches. We used a mixed quantum-classical approach developed by Skinner and coworkers to simulate the isotropic Raman-MCR spectrum of liquid water at 300 K. Our results illustrate that the intermolecular coupling leads to a broadening and redshift of the OH stretching band in a good agreement with experiment. Our theoretical analysis provides a molecular-level interpretation of Raman-MCR experiments on liquid water.<br/>

OH-stretch Raman multivariate curve resolution spectroscopy of HOD/H<sub>2</sub>O mixtures

2019 Spring National Meeting

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OH-stretch Raman multivariate curve resolution spectroscopy of HOD/H2O mixtures

OH-stretch Raman multivariate curve resolution spectroscopy of HOD/H₂O mixtures