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Efficient calculation of NMR isotopic shifts: Difference-dedicated vibrational perturbation theory

Journal article
Authors Jürgen Gräfenstein
Published in Journal of Chemical Physics
Volume 151
Issue 24
ISSN 0021-9606
Publication year 2019
Published at Department of Chemistry and Molecular Biology
Language en
Subject categories Quantum chemistry


We present difference-dedicated second-order vibrational perturbation theory (VPT2) as an efficient method for the computation of nuclear magnetic resonance (NMR) isotopic shifts, which reflect the geometry dependence of the NMR property in combination with different vibration patterns of two isotopologues. Conventional calculations of isotopic shifts, e.g., by standard VPT2, require scanning the geometry dependence over the whole molecule, which becomes expensive rapidly as the molecule size increases. In DD-VPT2, this scan can be restricted to a small region around the substitution site. At the heart of DD-VPT2 is a set of localized vibration modes common to the two isotopologues and designed such that the difference between the vibration patterns is caught by a small subset of them (usually fewer than 10). We tested the DD-VPT2 method for a series of molecules with increasing size and found that this method provides results with the same quality as VPT2 and in good agreement with the experiment, with computational savings up to 95% and less numerical instabilities. The method is easy to automatize and straightforward to generalize to other molecular properties.

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