Spin Component-Scaled Second-Order Møller−Plesset Perturbation Theory for Calculating NMR Shieldings
22-Dec-2014
J. Chem. Theory Comput., 2014, DOI: 10.1021/ct5007295, 11 (1), pp 37–44 published on 22.12.2014
J. Chem. Theory Comput., online article
J. Chem. Theory Comput., online article
Spin component-scaled and scaled opposite-spin second-order Møller–Plesset perturbation approaches (SCS-MP2 and SOS-MP2) are introduced for calculating NMR chemical shifts in analogy to the well-established scaled approaches for MP2 energies. Gauge-including atomic orbitals (GIAO) are employed throughout this work. The GIAO-SCS-MP2 and GIAO-SOS-MP2 methods typically show superior performance to nonscaled MP2 and are closer to the coupled-cluster singles doubles perturbative triples (CCSD(T))/cc-pVQZ reference values. In addition, the pragmatic use of mixed basis sets for the Hartree–Fock and the correlated part of NMR chemical shift calculations is shown to be beneficial.