Magnetic Optical Rotation from Real-Time Simulations in Finite Magnetic Fields

TL;DR

This paper introduces a real-time simulation method for magnetic optical rotation that tests the validity of Verdet's linear relation at high magnetic fields, revealing deviations above 10-20 kT and comparing different theoretical approaches.

Contribution

It develops a non-perturbative real-time simulation framework for magnetic optical rotation and evaluates the validity of linearity at ultra-high magnetic fields using advanced electronic-structure theories.

Findings

Verdet's linearity holds up to 10-20 kT.

Significant deviations occur above 20 kT.

The Tao-Perdew-Staroverov-Scuseria functional performs best among tested methods.

Abstract

We present a numerical approach to magnetic optical rotation based on real-time time-dependent electronic-structure theory. Not relying on perturbation expansions in the magnetic-field strength, the formulation allows us to test the range of validity of the linear relation between the rotation angle per unit path length and the magnetic-field strength that was established empirically by Verdet 160 years ago. Results obtained from time-dependent coupled-cluster and time-dependent current density-functional theory are presented for the closed-shell molecules H2, HF, and CO in magnetic fields up to 55 kT at standard temperature and pressure conditions. We find that Verdet's linearity remains valid up to roughly 10-20 kT, above which significant deviations from linearity are observed. Among the three current density-functional approximations tested in this work, the current-dependent Tao-Perdew-Staroverov-Scuseria hybrid functional performs the best in comparison with time-dependent coupled-cluster singles and doubles results for the magnetic optical rotation.