A theoretical study of intra-molecular vibrational effects on fractionation factors for molecules containing intra-molecular low-barrier hydrogen bonds

Travis S. Humble, Christopher J. Halkides, Jason D. Keltner, Michael Messina

Research output: Contribution to journalArticlepeer-review

2 Scopus citations

Abstract

The fractionation factor is defined as the equilibrium constant for the reaction; R-H+DOH ⇌ R-D+HOH. Of interest are values of fractionation factors that obtain for reactions where reactants and/or products form intra-molecular low-barrier hydrogen bonds. Experimentally measured isotopic fractionation factors are usually interpreted via a one-dimensional potential energy surface along the intrinsic proton hydrogen bond coordinate. Here we show that coupling the intrinsic proton coordinate to an intra-molecular vibrational mode has large effects on the values of isotopic fractionation factors and offer a picture for the fractionation factor for low-barrier hydrogen bonds based on the one-dimensional potential of mean force on the intrinsic proton coordinate.

Original languageEnglish
Pages (from-to)90-96
Number of pages7
JournalChemical Physics Letters
Volume289
Issue number1-2
DOIs
StatePublished - Jun 5 1998
Externally publishedYes

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