On the origin and contribution of the diamagnetic term in four-component relativistic calculations of magnetic properties

GUSTAVO A. AUCAR; TROND SAUE; LUUK VISSCHER; HANS J. JENSEN

JOURNAL OF CHEMICAL PHYSICS

AMER INST PHYSICS

Lugar: New York; Año: 1999 vol. 110 p. 6208 - 6218

0021-9606

The relativistic Dirac Hamiltonian that describes the motion of electrons in a magnetic field contains only paramagnetic terms ~i.e., terms linear in the vector potential A! while the corresponding nonrelativistic Schro¨dinger Hamiltonian also contains diamagnetic terms ~i.e., those from an A2 operator!. We demonstrate that all diamagnetic terms relativistically arise from second-order perturbation theory and that they correspond to a ‘‘redressing’’ of the electrons by the magnetic field. If the nonrelativistic limit is taken with a fixed no-pair Hamiltonian ~no redressing!, the diamagnetic term is missing. The Schro¨dinger equation is normally obtained by taking the nonrelativistic limit of the Dirac one-electron equation, we show why nonrelativistic use of the A2 operator is also correct in the many-electron case. In nonrelativistic approaches, diamagnetic terms are usually considered in first-order perturbation theory because they can be evaluated as an expectation value over the ground state wave function. The possibility of also using an expectation value expression, instead of a second-order expression, in the relativistic case is investigated. We also introduce and discuss the concept of ‘‘magnetically balanced’’ basis sets in relativistic calculations.