Ultrafast pump-probe and 2DIR anisotropy and temperature-dependent dynamics of liquid water within the E3B model

Recently, Tainter et al. [J. Chem. Phys. 134, 184501 (2011)] reparameterized a new rigid water model (E3B) that explicitly includes three-body interactions in its Hamiltonian. Compared to commonly used water models such as SPC/E and TIP4P, the new model shows better agreement with experiment for many physical properties including liquid density, melting temperature, virial coefficients, etc. However, the dynamics of the E3B model, especially as a function of temperature, has not been systematically evaluated. Experimental nonlinear vibrational spectroscopy is an ideal tool to study the dynamics of matter in condensed phases. In the present study, we calculate linear and nonlinear vibrational spectroscopy observables for liquid water using the E3B model at five temperatures: 10, 30, 50, 70 and 90 °C. Specifically, we calculate absorption and Raman spectra and pump-probe anisotropy for HOD in H2O at all temperatures, frequency-resolved pump-probe anisotropy for HOD in both H2O and D2O at 30 °C, and 2DIR anisotropy for HOD in D2O at 30 °C. In all cases, we find reasonable agreement with experiment, and for the ultrafast spectroscopy our results are a significant improvement over those of the SPC/E model. A likely reason for this improvement is that the three-body interaction terms in the E3B model are able to model cooperative hydrogen bonding. We also calculate rotational and frequency relaxation times at all temperatures, and fit the results to the Arrhenius equation. We find that the activation energy for hydrogen-bond switching in liquid water is 3.8 kcal/mol, which agrees well with the experimental value of 3.7 kcal/mol obtained from anisotropy decay experiments.