Transferability of vibrational spectroscopic map from TIP4P to TIP4P-like water models.

Abstract

We computed the IR, Raman, and sum frequency generation spectra of water in the OH-stretch region by employing the quantum/classical mixed approach that consists of a vibrational spectroscopic map and molecular dynamics (MD) simulation. We carried out the MD simulation with the TIP4P, TIP4P/2005, and TIP4P/Ice models and applied the map designed for TIP4P by Skinner et al. to each MD trajectory. Although the map is not tuned for TIP4P-like models, TIP4P/2005 and TIP4P/Ice provide the best reproduction of the experimental vibrational spectra of liquid water and crystalline ice, respectively. This result demonstrates the transferability of the map from TIP4P to TIP4P/2005 and TIP4P/Ice, meaning that one can choose an appropriate TIP4P-like model to calculate the vibrational spectra of an aqueous system without rebuilding the map.