Abstract

In this thesis, the theory of static magnetic resonance spectral parameters of nuclear magnetic resonance (NMR) and electron spin resonance (ESR) spectroscopy is investigated in terms of the molecular Breit-Pauli Hamiltonian, which is obtained from the relativistic Dirac equation via the Foldy-Wouthuysen transformation. A leading-order perturbational relativistic theory of NMR nuclear shielding and spin-spin coupling tensors, and ESR electronic g-tensor, is presented. In addition, the possibility of external magnetic-field dependency of NMR parameters is discussed.

Various first-principles methods of electronic structure theory and the role of one-electron basis sets and their performance in magnetic resonance properties in terms of their completeness profiles are discussed. The presented leading-order perturbational relativistic theories of NMR nuclear shielding tensors and ESR electronic g-tensors, as well as the theory of the magnetic-field dependent NMR shielding and quadrupole coupling are evaluated using first-principles wave function and density-functional theories.