IR and SFG vibrational spectroscopy of the water bend in the bulk liquid and at the liquid-vapor interface, respectively

Vibrational spectroscopy of the water bending mode has been investigated experimentally to study the structure of water in condensed phases. In the present work, we calculate the theoretical infrared (IR) and sum-frequency generation (SFG) spectra of the HOH bend in liquid water and at the water liq...

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Bibliographic Details
Published in:The Journal of chemical physics 2015-07, Vol.143 (1), p.014502-014502
Main Authors: Ni, Yicun, Skinner, J L
Format: Article
Language:English
Subjects:
COMPARATIVE EVALUATIONS
Computer simulation
Coupling (molecular)
DIPOLES
Fluid dynamics
HYDROGEN
Infrared spectroscopy
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
INTERACTIONS
LIQUIDS
Molecular dynamics
MOLECULAR DYNAMICS METHOD
MOLECULES
Physical simulation
Physics
POLARIZABILITY
SIMULATION
SPECTRA
SPECTRAL DENSITY
SPECTROSCOPY
Spectrum analysis
SURFACES
VAPORS
WATER
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Summary:Vibrational spectroscopy of the water bending mode has been investigated experimentally to study the structure of water in condensed phases. In the present work, we calculate the theoretical infrared (IR) and sum-frequency generation (SFG) spectra of the HOH bend in liquid water and at the water liquid/vapor interface using a mixed quantum/classical approach. Classical molecular dynamics simulation is performed by using a recently developed water model that explicitly includes three-body interactions and yields a better description of the water surface. Ab-initio-based transition frequency, dipole, polarizability, and intermolecular coupling maps are developed for the spectral calculations. The calculated IR and SFG spectra show good agreement with the experimental measurements. In the theoretical imaginary part of the SFG susceptibility for the water liquid/vapor interface, we find two features: a negative band centered at 1615 cm(-1) and a positive band centered at 1670 cm(-1). We analyze this spectrum in terms of the contributions from molecules in different hydrogen-bond classes to the SFG spectral density and also compare to SFG results for the OH stretch. SFG of the water bending mode provides a complementary picture of the heterogeneous hydrogen-bond configurations at the water surface.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.4923462