Due to the largely empirical nature of interpreting NMR spectra, first principles calculations have become extremely useful for assigning the chemical shift peaks and J-couplings to specific nuclei. We demonstrate an accurate, scalable numeric atom-centered orbital (NAO) based implementation for the computation of molecular NMR shieldings, nuclear J-couplings, and magnetizabilities based on density functional theory. Good convergence of the NAO basis sets is demonstrated by comparing the computed shieldings and magnetizabilities to a set of Gaussian type orbital (GTOs) basis sets. For J-couplings, the key issue is basis set flexiblity in the atomic core region. Here we follow the approach pursued by Jensen’s pcJ-n GTO basis sets (one of the most accurate GTO basis sets for J-couplings) and develop a similarly accurate class of NAO basis sets, dubbed NAO-J-n. Large scale applicability is demonstrated by calculating the shieldings and J-couplings for a system of over a 1000 atoms.

Large-scale first principles NMR calculations with numeric atom-centered basis sets

255th National Meeting (2018)

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