Self-consistent perturbation theory of diamagnetism

Abstract

An ab initio gauge-invariant molecular orbital theory is developed for nuclear magnetic shielding. The molecular orbitals are written as linear combinations of gauge-invariant atomic orbitals, the wavefunctions in the presence of a uniform external magnetic field being determined by self-consistent field perturbation theory. The final magnetic shielding result is broken up into contributions which can be related to various features of electronic structure. Calculated magnetic shielding constants are presented using three sets of atomic orbitals, all of which are taken as contracted gaussian-type functions. The first two sets are minimal and the third is slightly extended. All three levels of theory give good descriptions of shielding at first row and hydrogen atoms. Carbon and hydrogen chemical shifts calculated at the extended level are in excellent agreement with experimental values.