Applicability of self-consistent reaction field (SCRF) method to DFT estimation of hydrogen isotope separation factors in reversible processes

In earlier quantum chemical calculations of isotope effects, chemical species in the liquid phase were generally treated as existing in the gas phase. In recent years, however, advances in computational programs have made it easier for the self-consistent reaction field (SCRF) method to handle chemi...

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Bibliographic Details
Published in:Isotopes in environmental and health studies 2024-05, Vol.60 (3), p.272-285
Main Authors: Yanase, Satoshi, Kikawada, Yoshikazu, Oi, Takao
Format: Article
Language:English
Subjects:
Anharmonicity
chemical interactions
Chemical speciation
chemical species
density functional theory (DFT)
Dimers
Hydrogen
Hydrogen isotopes
Isotope effect
Isotope separation
isotopes
Isotopic enrichment
Liquid phases
liquids
Quantum chemistry
quantum mechanics
reversible process
self-consistent reaction field (SCRF)
separation factor
theory
Vapor phases
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Summary:In earlier quantum chemical calculations of isotope effects, chemical species in the liquid phase were generally treated as existing in the gas phase. In recent years, however, advances in computational programs have made it easier for the self-consistent reaction field (SCRF) method to handle chemical species in the liquid phase, and as a result, it has become easier to apply the SCRF method to isotope effect calculations. This paper concerns the scope of application of the DFT-SCRF method to reversible processes for hydrogen isotope enrichment. It is found that the applicability of the method depends on the type of the intermolecular interaction in the liquid phase and the degree of hydrogen isotope effect (separation factor) on which the process is based. When the magnitude of the isotope effect of the separation system is greater than 10 -1 , the simple SCRF method is fully applicable; when the magnitude is around 10 -2 , SCRF with a dimer model, in which the monomer is replaced by a dimer, is applicable for the analysis of the liquid phase with relatively strong intermolecular interactions. Anharmonic correction to the separation factor calculated based on harmonic frequencies may be effective to systems with the liquid phase with weak intermolecular interactions.
ISSN:1025-6016
1477-2639
1477-2639
DOI:10.1080/10256016.2024.2336470