An electronic Hamiltonian for origin independent calculations of magnetic properties

Abstract

A gauge origin independent formalism for the calculation of molecular magnetic properties is presented. Origin independence is obtained by using London’s gauge invariant atomic orbitals, expanding the second quantization Hamiltonian in the external magnetic field and nuclear magnetic moments, and using the resulting expansion terms as perturbation operators in response function calculations. To ensure orthonormality of the molecular orbitals, a field-dependent symmetrical orthonormalization is employed. In this way the gauge dependence of the London orbitals is transferred to the Hamiltonian. The resulting perturbation operators may be used to calculate magnetic properties from any approximate ab initio wave function.