Infrared spectra of ice and water from first principles: intra vs. intermolecular dipole correlations

ORAL

Abstract

We report simulated infrared (IR) spectra of deuterated ice and water using Car-Parrinello molecular dynamics with maximally localized Wannier functions. Experimental features of both ice and water are accurately reproduced within the harmonic approximation. Calculated line shapes are further decomposed in terms of intra and intermolecular dipole correlation functions with spatial resolution. This approach proves to be very useful to understand the origin of spectral features and the nature of the underlying hydrogen-bond (H-bond) network. We find that intermolecular dynamic charge fluctuations play a crucial role over the entire frequency range.

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Authors

  • Wei Chen

    Department of Physics, Princeton University, Princeton, NJ 08544, USA

  • Manu Sharma

    Department of Chemistry, University of California, Davis, CA 95616, USA, UC Davis

  • Raffaele Resta

    University of Trieste, Dipartimento di Fisica Teorica, Universit\`a di Trieste, Strada Costiera 11, 34014 Trieste, Italy

  • Giulia Galli

    University of California-Davis, UC Davis, Department of Chemistry, University of California, Davis, University of California, Davis, Department of Chemistry, University of California, Davis, CA 95616, USA, University of California Davis

  • Roberto Car

    Dept. of Chemistry, Princeton University, Department of Chemistry, Princeton University, Princeton, NJ 08544, USA, Chemistry Department, Princeton University, Princeton, NJ