Excited States of Molecules in Strong Uniform and Nonuniform Magnetic Fields.

Abstract

This paper reports an implementation of Hartree-Fock linear response with complex orbitals for computing electronic spectra of molecules in strong external magnetic fields. The implementation is completely general, allowing for spin-restricted, spin-unrestricted, and general two-component reference states. The method is applied to small molecules placed in strong uniform and nonuniform magnetic fields of astrochemical importance at the Random Phase Approximation level of theory. For uniform fields, where comparison is possible, the spectra are found to be qualitatively similar to those recently obtained with equation of motion coupled cluster theory. We also study the behavior of spin-forbidden excitations with progressive loss of spin symmetry induced by nonuniform magnetic fields. Finally, the equivalence of length and velocity gauges for oscillator strengths when using complex orbitals is investigated and found to hold numerically.