Dielectric properties of condensed systems composed of fragments
arXiv:1807.06326 · doi:10.1063/1.5044636
Abstract
The dielectric properties of molecules or nanostructures are usually modified in a complex manner, when assembled into a condensed phase. We propose a first-principles method to compute polarizabilities of sub-entities of solids and liquids, which accounts for multipolar interactions at all orders, and is applicable to any semiconductor or insulator. The method only requires the evaluation of induced fields in the condensed phase, with no need of multiple calculations for each constituent. As an example, we present results for the molecular polarizabilities of water in a wide pressure and temperature range. We found that at ambient conditions, the dipole-induced-dipole approximation is sufficiently accurate and the Clausius-Mossotti relation may be used, e.g. to obtain molecular polarizabilities from experimental refractive indexes. However with increasing pressure this approximation becomes unreliable and in the case of ice X the Clausius-Mossotti relation is not valid.
arXiv comment16 pages, 4 figures, 1 table
References in corpus (7)
- Phonons and related properties of extended systems from density-functional perturbation theory
- Maximally localized Wannier functions: Theory and applications
- Perspective: Advances and challenges in treating van der Waals dispersion forces in density functional theory
- A First-Principles Approach to Insulators in Finite Electric Fields
- The refractive index and electronic gap of water and ice increase with increasing pressure
- A Local Representation of the Electronic Dielectric Response Function
- Molecular Polarizability of Water from the Local Dielectric Response Theory