Assessing the electric-field approximation to IR and Raman spectra of dilute HOD in D2O

We analyze the validity of the commonly used electric-field (E-field) approximation to vibrational OH stretch Raman spectra of dilute HOD in D(2)O by computing the OH stretch frequency of all molecules in several different structure models, each containing around 2000 molecules. The calculations are done at the B3LYP level using clusters containing 32 molecules centered around the molecule for which the frequencies are calculated; the large cluster size is required due to significant nonlocal contributions influencing the computed frequencies. The vibrational frequencies are determined using a six-point potential optimized discrete variable representation. Raman and infrared intensities are furthermore computed to generate the spectra. We find that a quadratic fit of E-field versus frequency gives a reasonable representation of the calculated distribution of frequencies. However, the mapping depends significantly on the structural model and is thus not universal. Anharmonic couplings are calculated for several optimized clusters showing a general trend to compress the computed frequency distributions, which is in agreement with dynamical simulations (motional narrowing).