  Second-harmonic scattering experiments of water and other bulk molecular
liquids have long been assumed to be insensitive to interactions between the
molecules. The measured intensity is generally thought to arise from incoherent
scattering due to individual molecules. We introduce a method to compute the
second-harmonic scattering pattern of molecular liquids directly from atomistic
computer simulations, which takes into account the coherent terms. We apply
this approach to large-scale molecular dynamics simulations of liquid water,
where we show that nanosecond second-harmonic scattering experiments contain a
coherent contribution arising from radial and angular correlations on a length
scale of < 1 nm, much shorter than had been recently hypothesized (Shelton, D.
P. J. Chem. Phys. 2014, 141). By combining structural correlations from
simulations with experimental data (Shelton, D. P. J. Chem. Phys. 2014, 141),
we can also extract an effective molecular hyperpolarizability in the liquid
phase. This work demonstrates that second-harmonic scattering experiments and
atomistic simulations can be used in synergy to investigate the structure of
complex liquids, solutions, and biomembranes, including the intrinsic
intermolecular correlations.
