Magnetic optical rotation from real-time simulations in finite magnetic fields

Benedicte Sverdrup Ofstad; Meilani Wibowo-Teale; Håkon Emil Kristiansen; Einar Aurbakken; Marios Petros Kitsaras; Øyvind Sigmundson Schøyen; Eirill Hauge; Tom J P Irons; Simen Kvaal; Stella Stopkowicz; Andrew M Wibowo-Teale; Thomas Bondo Pedersen

doi:10.1063/5.0171927

Magnetic optical rotation from real-time simulations in finite magnetic fields

J Chem Phys. 2023 Nov 28;159(20):204109. doi: 10.1063/5.0171927.

Authors

Affiliations

¹ Hylleraas Centre for Quantum Molecular Sciences, Department of Chemistry, University of Oslo, Oslo, Norway.
² School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, United Kingdom.
³ Physical and Theoretical Chemistry, Saarland University, Campus B2.2, 66123 Saarbruecken, Germany.
⁴ Department of Physics, University of Oslo, Oslo, Norway.
⁵ Department of Numerical Analysis and Scientific Computing, Simula Research Laboratory, 0164 Oslo, Norway.

PMID: 38018753
DOI: 10.1063/5.0171927

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.