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research article

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

Tocci, Gabriele  
•
Liang, Chungwen  
•
Wilkins, David M.  
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2016
The Journal of Physical Chemistry Letters

econd-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.

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Type
research article
DOI
10.1021/acs.jpclett.6b01851
Web of Science ID

WOS:000387205000012

Author(s)
Tocci, Gabriele  
Liang, Chungwen  
Wilkins, David M.  
Roke, Sylvie  
Ceriotti, Michele  
Date Issued

2016

Publisher

Amer Chemical Soc

Published in
The Journal of Physical Chemistry Letters
Volume

7

Issue

21

Start page

4311

End page

4316

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
LBP  
COSMO  
Available on Infoscience
November 29, 2016
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/131671
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