Second-Harmonic Scattering as a Probe of Structural Correlations in Liquids

Gabriele Tocci*, Chungwen Liang, David M. Wilkins, Sylvie Roke, Michele Ceriotti

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

15 Citations (Scopus)


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.

Original languageEnglish
Pages (from-to)4311-4316
Number of pages6
JournalJournal of Physical Chemistry Letters
Issue number21
Publication statusPublished - 11 Oct 2016


  • Nonlinear Light Scattering
  • Molecular Dynamics
  • Water

ASJC Scopus subject areas

  • Materials Science(all)
  • Physical and Theoretical Chemistry


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