Comprehensive Quantum Calculation of the First Dielectric Virial Coefficient of Water

Published

January 12, 2024

Author(s)

Giovanni Garberoglio, Chiara Lissoni, Luca Spagnoli, Allan H. Harvey

Abstract

We present a complete calculation, fully accounting for quantum effects and for molecular flexibility, of the first dielectric virial coefficient of water and its isotopologues. The contribution of the electronic polarizability is computed from a state-of-the-art intramolecular potential and polarizability surface from the literature, and its small temperature dependence is quantified. The dipolar polarizability is calculated in a similar manner with an accurate literature dipole-moment surface; it differs from the classical result both due to the different molecular geometries sampled at different temperatures and due to the quantization of rotation. We calculate the dipolar contribution independently from spectroscopic information in the HITRAN2020 database and find that the two methods yield consistent results. The resulting first dielectric virial coefficient provides a complete description of the dielectric constant at low density that can be used in humidity metrology and as a boundary condition for new formulations for the static dielectric constant of water and heavy water.

Citation

Journal of Chemical Physics

Volume

160

Issue

2

Pub Type

Journals

Download Paper

https://doi.org/10.1063/5.0187774

Local Download

Keywords

dielectric constant, heavy water, polarizability, virial coefficient, water

Citation

Garberoglio, G. , Lissoni, C. , Spagnoli, L. and Harvey, A. (2024), Comprehensive Quantum Calculation of the First Dielectric Virial Coefficient of Water, Journal of Chemical Physics, [online], https://doi.org/10.1063/5.0187774, https://tsapps.nist.gov/publication/get_pdf.cfm?pub_id=956903 (Accessed October 6, 2025)