A simulation study of the optical Kerr effect in liquid water

A molecular dynamics simulation study is presented for the dynamics of the polarizability anisotropy of liquid water using the SPC/E model and a dipolar induction scheme that involves the intrinsic polarizability and first hyperpolarizability tensors obtained from ab initio quantum chemical calculations at the MP2/6- 311++G(d, p) level. The time-correlation functions for the collective polarizability anisotropy, the optical Kerr effect response, and the frequency spectra are analyzed in terms of the intrinsic and induced polarizability contributions. At short times, the simulated Kerr nuclear response exhibits maxima near 15, 50 and 180 fs, followed by a diffusive tail which has been fitted by a bi-exponential with time constants ca. 0.4 and 2.5 ps. The short time features are in good agreement with available simulation and experimental results. The agreement with experiments is less satisfactory for the diffusive components. The main features of the frequency spectrum include a rotational-diffusion peak centered around 3 cm(-1), a collision-induced ( hindered translations) band near 200 cm(-1), and a broad librational band at 450 cm(-1). The simulation results are in good agreement with experimental frequency spectra obtained from Kerr effect and related spectroscopies, but fail to reproduce the experimental band near 60 cm(-1).