Calculation of secondary β-deuterium equilibrium isotope effects on protonation and deprotonation of methanol and methanediol

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Abstract

Secondary β-deuterium equilibrium isotope effects are calculated for protonation and deprotonation of methanol and of methanediol using ab initio quantum-mechanical methods. Improved results are obtained by multiplying all calculated force constants by a single empirical scaling factor. Scaled 4-31G force constants enable isotope effects to be calculated reliably whereas use of the STO-3G basis may lead to incorrect predictions. Calculated geometries, force constants and isotope effects may be rationalised successfully by the theory of negative hyperconjugation.

Original languageEnglish
Pages (from-to)105-117
Number of pages13
JournalJournal of Molecular Structure: THEOCHEM
Volume105
Issue number1-2
DOIs
Publication statusPublished - 1 Nov 1983

ASJC Scopus subject areas

  • Biochemistry
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

Cite this

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title = "Calculation of secondary β-deuterium equilibrium isotope effects on protonation and deprotonation of methanol and methanediol",
abstract = "Secondary β-deuterium equilibrium isotope effects are calculated for protonation and deprotonation of methanol and of methanediol using ab initio quantum-mechanical methods. Improved results are obtained by multiplying all calculated force constants by a single empirical scaling factor. Scaled 4-31G force constants enable isotope effects to be calculated reliably whereas use of the STO-3G basis may lead to incorrect predictions. Calculated geometries, force constants and isotope effects may be rationalised successfully by the theory of negative hyperconjugation.",
author = "Williams, {Ian H.}",
year = "1983",
month = "11",
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doi = "10.1016/0166-1280(83)80037-2",
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pages = "105--117",
journal = "Journal of Molecular Structure : THEOCHEM",
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N2 - Secondary β-deuterium equilibrium isotope effects are calculated for protonation and deprotonation of methanol and of methanediol using ab initio quantum-mechanical methods. Improved results are obtained by multiplying all calculated force constants by a single empirical scaling factor. Scaled 4-31G force constants enable isotope effects to be calculated reliably whereas use of the STO-3G basis may lead to incorrect predictions. Calculated geometries, force constants and isotope effects may be rationalised successfully by the theory of negative hyperconjugation.

AB - Secondary β-deuterium equilibrium isotope effects are calculated for protonation and deprotonation of methanol and of methanediol using ab initio quantum-mechanical methods. Improved results are obtained by multiplying all calculated force constants by a single empirical scaling factor. Scaled 4-31G force constants enable isotope effects to be calculated reliably whereas use of the STO-3G basis may lead to incorrect predictions. Calculated geometries, force constants and isotope effects may be rationalised successfully by the theory of negative hyperconjugation.

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