Computation of deuterium isotope perturbation of 13C NMR chemical shifts of alkanes: A local mode zero-point level approach

Kin S. Yang, Bruce Hudson

Research output: Contribution to journalArticlepeer-review

8 Scopus citations

Abstract

Replacement of H by D perturbs the 13C NMR chemical shifts of an alkane molecule. This effect is largest for the carbon to which the D is attached, diminishing rapidly with intervening bonds. The effect is sensitive to stereochemistry and is large enough to be measured reliably. A simple model based on the ground (zero point) vibrational level and treating only the C-H(D) degrees of freedom (local mode approach) is presented. The change in CH bond length with H/D substitution as well as the reduction in the range of the zero-point level probability distribution for the stretch and both bend degrees of freedom are computed. The 13C NMR chemical shifts are computed with variation in these three degrees of freedom, and the results are averaged with respect to the H and D distribution functions. The resulting differences in the zero-point averaged chemical shifts are compared with experimental values of the H/D shifts for a series of cycloalkanes, norbornane, adamantane, and protoadamantane. Agreement is generally very good. The remaining differences are discussed. The proton spectrum of cyclohexane- is revisited and updated with improved agreement with experiment.

Original languageEnglish (US)
Pages (from-to)12283-12290
Number of pages8
JournalJournal of Physical Chemistry A
Volume114
Issue number46
DOIs
StatePublished - Nov 25 2010

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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