Since the vibrational frequencies of a water molecule are particularly sensitive to the surrounding environment, vibrational spectroscopy has become a powerful tool for characterizing both molecular structure and dynamics of aqueous systems from the gas to the condensed phase. However, a unique assignment of the spectra measured for water under different conditions and in different environments is nontrivial due to the fluctuating behavior of the underlying hydrogen-bond network, which gives rise to several (homogeneously and/or inhomogeneously broadened) features that are often difficult to interpret. In this talk, I present an integrated theoretical and computational framework (called many-body molecular dynamics or MB-MD) that enables an accurate modeling of the vibrational spectra of water from rigorous many-body representations of the potential energy, dipole moment, and polarizability surfaces combined with a quantum-mechanical treatment of the nuclear motion. I will discuss specific MB-MD applications to water clusters in the gas phase, liquid water, and the air/water interface.

Dissecting the vibrational spectra of water from the gas to the condensed phase through many-body molecular dynamics simulations

251st National Meeting (2016)

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