Asymmetry of the Electrostatic Environment as the Origin of the Symmetry Breaking Effect of the Nitrate Ion in Aqueous Solution

Elucidating the mechanism of how vibrational modes are affected by intermolecular interactions is important for a better understanding of the nature of the former as probes of the latter. Here, such an analysis is carried out for the N-O stretching modes of the nitrate ion interacting with water, with an emphasis on the symmetry breaking effect. On the basis of theoretical calculations on the structural, vibrational, and electrostatic properties of molecular clusters and spectral simulations for an aqueous solution, a transparent view is demonstrated on the mechanism that modulations of spatially local electrostatic environment give rise to structural and spectroscopic symmetry breaking effect. The electrostatic interaction model constructed here is a seven-parameter model; the use of a single electrostatic parameter, such as the electric field on a single atomic site, is found to be insufficient for quantitative evaluation. It is also shown that the frequency modulations of the N-O stretching modes in aqueous solution occur on a time scale much shorter than 0.1 ps.