Liquid water dynamical partial charges and infrared intensities
Résumé
In this paper we present a study of the atomic polar tensors (APT) and dynamical charges in liquid water. An exact sum rule is used to relate dynamical partial charges to the total intensity of the infrared (IR) spectrum. It was then possible to evaluate, from experimental data, these charges through isotopic substitution data. These were compared with calculated values from a Density Functional Theory based first-principle simulations and both show an hydrogen charge increase when going from the gas phase to the liquid phase, as expected. The hydrogen APT tensor is then studied in more details from simulation and shown to be highly anisotropic, a feature attributed to the electronic nature of the hydrogen bond. The anisotropy of the hydrogen APT tensor is finally related to the ratio of IR band intensities in liquid water.
Domaines
Chimie théorique et/ou physique
Origine : Fichiers produits par l'(les) auteur(s)
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