The impact of the vibrational coupling of the OH stretch mode on the spectra differs significantly between IR and Raman spectra of water. Unified understanding of the vibrational couplings is not yet achieved. By using a different class of vibrational spectroscopy, hyper-Raman (HR) spectroscopy, together with machine-learning-assisted HR spectra calculation, we examine the impact of the vibrational couplings of water through the comparison of isotopically diluted HO and pure HO. We found that the isotopic dilution reduces the HR bandwidths, but the impact of the vibrational coupling is smaller than in the IR and parallel-polarized Raman. Machine learning HR spectra indicate that the intermolecular coupling plays a major role in broadening the bandwidth, while the intramolecular coupling is negligibly small, which is consistent with the IR and Raman spectra. Our result clearly demonstrates a limited impact of the intramolecular vibration, independent of the selection rules of vibrational spectroscopies.
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