Predicting the Raman Spectra of Liquid Water with a Monomer-Field Model

RA Lacour and JP Heindel and T Head-Gordon, JOURNAL OF PHYSICAL CHEMISTRY LETTERS, 14, 11742-11749 (2023).

DOI: 10.1021/acs.jpclett.3c02873

The Raman spectrum of liquid water is quite complex, reflecting its strong sensitivity to the local environment of the individual waters. The OH-stretch region of the spectrum, which captures the influence of hydrogen bonding, has only just begun to be unraveled. Here we develop a model for predicting the Raman spectra of the OH-stretch region by considering how local electric fields distort the energy surface of each water monomer. We find that our model is capable of reproducing the bimodal nature of the main peak, with the shoulder at 3250 cm(-1) resulting almost entirely from Fermi resonance. Furthermore, we capture the temperature and polarization dependence of the shoulder, which has proven to be difficult to obtain with previous methods, and analyze the origin of this dependence. We expect our model to be generally useful for understanding and predicting how Raman spectra change under different conditions and with different probe reporters beyond water.

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