Definitive Benchmark Study of Ring Current Effects on Amide Proton Chemical Shifts
Anders S. Christensen
*, Stephan P. A. Sauer, and Jan H. Jensen
*
Department of Chemistry, University of Copenhagen, Universitetsparken 5, DK-2100 Copenhagen Ø, Denmark
J. Chem. Theory Comput., 2011, 7 (7), pp 2078–2084
Abstract (the paper is summarized in the video at the end of the post)
The ring current effect on chemical shifts of amide protons (ΔδRC) is computed at the B3LYP/6-311++G(d,p)//B3LYP/aug-cc-pVTZ level of theory for 932 geometries of dimers of N-methylacetamide and aromatic amino acid side chains extracted from 21 different proteins. These ΔδRC
values are scaled by 1.074, based on MP2/cc-pVQZ//B3LYP/aug-cc-pVTZ
chemical shift calculations on four representative formamide/benzene
dimers, and are judged to be accurate to within 0.1 ppm based on
CCSD(T)/CBS//B3LYP/aug-cc-pVTZ calculations on formamide. The 932 scaled
ΔδRC values are used to benchmark three empirical ring
current models, including the Haigh–Mallion model used in the SPARTA,
SHIFTX, and SHIFTS chemical shift prediction codes. Though the RMSDs for
these three models are below 0.1 ppm, deviations up to 0.29 ppm are
found, but these can be decreased to below 0.1 ppm by changing a single
parameter. The simple point-dipole model is found to perform just as
well as the more complicated Haigh–Mallion and Johnson–Bovey models.
The paper Instructions on how I made the video will appear in a future post. In the mean time, enjoy!