Benchmarking Hydrogen and Carbon NMR Chemical Shifts at HF, DFT, and MP2 Levels

J. Chem. Theory Comput., 2014, DOI: 10.1021/ct400780f, 10 (2), pp 572–578 published on 23.01.2014

J. Chem. Theory Comput., online article

An extensive study of error distributions for calculating hydrogen and carbon NMR chemical shifts at Hartree–Fock (HF), density functional theory (DFT), and Møller–Plesset second-order perturbation theory (MP2) levels is presented. Our investigation employs accurate CCSD(T)/cc-pVQZ calculations for providing reference data for 48 hydrogen and 40 carbon nuclei within an extended set of chemical compounds covering a broad range of the NMR scale with high relevance to chemical applications, especially in organic chemistry. Besides the approximations of HF, a variety of DFT functionals, and conventional MP2, we also present results with respect to a spin component-scaled MP2 (GIAO-SCS-MP2) approach. For each method, the accuracy is analyzed in detail for various basis sets, allowing identification of efficient combinations of method and basis set approximations.

TU München
Helmholtz München
MPI of Neurobiology
MPI of Biochemistry