An ab Initio Linear Response Method for Computing Magnetic Circular Dichroism Spectra with Nonperturbative Treatment of Magnetic Field.

Abstract

Magnetic circular dichroism (MCD) experiments provide a sensitive tool for exploring geometric, magnetic, and electronic properties of chemical complexes and condensed matter systems. They are also challenging to simulate because of the need to simultaneously treat the perturbations of a finite magnetic field as well as an optical field. In this work, we introduce an ab initio approach that treats the external magnetic field nonperturbatively with London orbitals for simulating the MCD spectra of closed-shell systems. Effects of a magnetic field are included variationally in the spin-free nonrelativistic Hamiltonian, followed by a linear response formalism to directly calculate the difference in absorption between the left and right circularly polarized light. In addition to the presentation of underlying mathematical formalism and implementation, the method developed in this paper has been applied to simulations of MCD spectra of the sodium anion, 2,2,6,6-tetramethylcyclohexanone, and 3-methyl-2-hexanone. Results are discussed and compared to experiments.