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Phys. Rev. B 77, 245114 (2008) [5 pages]

Role of dipolar correlations in the infrared spectra of water and ice

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Wei Chen1, Manu Sharma2, Raffaele Resta3,4, Giulia Galli2, and Roberto Car1,5,6
1Department of Physics, Princeton University, Princeton, New Jersey 08544, USA
2Department of Chemistry, University of California, Davis, California 95616, USA
3INFM DEMOCRITOS National Simulation Center, via Beirut 2, 34014 Trieste, Italy
4Dipartimento di Fisica Teorica, Università di Trieste, Strada Costiera 11, 34014 Trieste, Italy
5Department of Chemistry, Princeton University, Princeton, New Jersey 08544, USA
6Princeton Institute for the Science and Technology of Materials, Princeton University, Princeton, New Jersey 08544, USA

Received 21 April 2008; published 13 June 2008

We report simulated infrared (IR) spectra of deuterated water and ice using Car–Parrinello molecular dynamics with maximally localized Wannier functions. Experimental features are accurately reproduced within the harmonic approximation. By decomposing the line shapes in terms of intramolecular and intermolecular dipole correlation functions, we find that short-range intermolecular dynamic charge fluctuations associated to hydrogen bonds are prominent over the entire spectral range. Our analysis reveals the origin of several spectral features and identifies network bending modes in the far IR range.

© 2008 The American Physical Society

URL:
http://link.aps.org/doi/10.1103/PhysRevB.77.245114
DOI:
10.1103/PhysRevB.77.245114
PACS:
36.20.Ng, 71.15.Pd, 32.10.Dk, 78.20.Ci