First-Principles Diffusivity Ratios for Atmospheric Isotope Fractionation on Mars and Titan
Publication date
2021-04-01
Document type
Research article
Author
Harvey, Allan H.
Organisational unit
Scopus ID
Series or journal
Journal of Geophysical Research: Planets
Periodical volume
126
Periodical issue
4
Peer-reviewed
✅
Part of the university bibliography
✅
Keyword
Diffusion
First-principles calculations
Isotope fractionation
Kinetic theory
Methane
Water
Abstract
Recent work used the kinetic theory of molecular gases, along with state-of-the-art intermolecular potentials, to calculate from first principles the diffusivity ratios necessary for modeling kinetic fractionation of water isotopes in air. Here, we extend that work to the Martian atmosphere, employing potential-energy surfaces for the interaction of water with carbon dioxide and with nitrogen. We also derive diffusivity ratios for methane isotopes in the atmosphere of Titan by using a high-quality potential for the methane-nitrogen pair. The Mars calculations cover 100–400 K, while the Titan calculations cover 50–200 K. Surprisingly, the simple hard-sphere theory that is inaccurate for Earth's atmosphere is in good agreement with the rigorous results for the diffusion of water isotopes in the Martian atmosphere. A modest disagreement with the hard-sphere results is observed for the diffusivity ratio of CH3D in the atmosphere of Titan. We present temperature-dependent correlations, as well as estimates of uncertainty, for the diffusivity ratios involving HDO, H217O, and H218O in the Martian atmosphere, and for CH3D and 13CH4 in the atmosphere of Titan, providing for the first time the necessary data to be able to model kinetic isotope fractionation in these environments.
Version
Not applicable (or unknown)
Access right on openHSU
Metadata only access
Open Access Funding
Wiley (DEAL)