Molecular Origin of the Vibrational Structure of Ice Ih

An unambiguous assignment of the vibrational spectra of ice Ih remains a matter of debate. This study demonstrates that an accurate representation of many-body interactions between water molecules, combined with an explicit treatment of nuclear quantum effects through many-body molecular dynamics (M...

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Bibliographic Details
Published in:The journal of physical chemistry letters 2017-06, Vol.8 (12), p.2579-2583
Main Authors: Moberg, Daniel R, Straight, Shelby C, Knight, Christopher, Paesani, Francesco
Format: Article
Language:English
Subjects:
ice
INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
many-body effects
molecular dynamics
nuclear quantum effects
vibrational spectroscopy
water
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Summary:An unambiguous assignment of the vibrational spectra of ice Ih remains a matter of debate. This study demonstrates that an accurate representation of many-body interactions between water molecules, combined with an explicit treatment of nuclear quantum effects through many-body molecular dynamics (MB-MD), leads to a unified interpretation of the vibrational spectra of ice Ih in terms of the structure and dynamics of the underlying hydrogen-bond network. All features of the infrared and Raman spectra in the OH stretching region can be unambiguously assigned by taking into account both the symmetry and the delocalized nature of the lattice vibrations as well as the local electrostatic environment experienced by each water molecule within the crystal. The high level of agreement with experiment raises prospects for predictive MB-MD simulations that, complementing analogous measurements, will provide molecular-level insights into fundamental processes taking place in bulk ice and on ice surfaces under different thermodynamic conditions.
ISSN:1948-7185
1948-7185
DOI:10.1021/acs.jpclett.7b01106