Microheterogeneity in Liquid Water Associated with Hydrogen-Bond Cooperativity-IR Spectroscopic and MD Simulation Study of Temperature Effect

Structural microheterogeneity arising from the cooperative nature of hydrogen bonding is a critical yet often overlooked factor in the mechanistic understanding of physicochemical and biological processes occurring in aqueous environments. MD simulations using a potential that accounts for molecular flexibility and directional interactions revealed inhomogeneity arising from patches of continuously connected, four-bonded molecules embedded within a less ordered, space-filling hydrogen-bond network. The size of these patches follows a statistical distribution that is strongly temperature-dependent. With increasing temperature, the average size of the patches decreases, whereas the contribution of molecules forming the inter-patch zones becomes more pronounced. The nature of microheterogeneity is evidenced by temperature-dependent changes in the asymmetry of calculated power spectra as well as in the measured IR absorption within the stretching, bending, and combination band regions. A novel method for band analysis incorporates the calculation of skewness and a mirroring procedure for more accurate determination of FWHM of asymmetric bands. Discontinuities in the temperature dependence of spectral parameters observed within the 5-80 °C range correspond to the thermodynamic anomalies of liquid water. We show that structural microheterogeneity persists near 100 °C, suggesting that aqueous processes are better described by statistical distributions than by uniform models. Molecular simulations and IR spectroscopy offer key insights into these distributions.