Modeling Ultrafast Electron Dynamics in Strong Magnetic Fields Using Real-Time Time-Dependent Electronic Structure Methods

Wibowo, Meilani; Irons, Tom J. P.; Teale, Andrew M.

Abstract

An implementation of real-time time-dependent Hartree-Fock (RT-TDHF) and current-density-functional theory (RT-TDCDFT) for molecules in strong uniform magnetic fields is presented. In contrast to earlier implementations, the present work enables the use of the RT-TDCDFT formalism, which explicitly includes field dependent terms in the exchange-correlation functional. A range of current dependent exchange-correlation functionals based on the TPSS functional are considered, including a range-separated variant, which is particularly suitable for application to excited state calculations. The performance of a wide range of propagator algorithms for real-time methods is investigated in this context. A recently proposed molecular orbital pair decomposition analysis allows for assignment of electronic transitions, providing detailed information about which molecular orbitals are involved in each excitation. 1 The application of these methods is demonstrated for the electronic absorption spectra of N 2 and H 2 O both in the absence and in the presence of a magnetic field. The dependence of electronic spectra on the magnetic field strength and its orientation relative to the molecule is studied. The complex evolution of the absorption spectra with magnetic field is rationalised using the molecular orbital pair decomposition analysis, which provides crucial insight in strong fields where the spectra are radically different from their zero-field counterparts.

Citation

Wibowo, M., Irons, T. J. P., & Teale, A. M. (2021). Modeling Ultrafast Electron Dynamics in Strong Magnetic Fields Using Real-Time Time-Dependent Electronic Structure Methods. Journal of Chemical Theory and Computation, 17(4), 2137-2165. https://doi.org/10.1021/acs.jctc.0c01269

• Journal Article Type: Article
• Acceptance Date: Jan 25, 2021
• Online Publication Date: Mar 16, 2021
• Publication Date: Mar 16, 2021
• Deposit Date: Feb 3, 2021
• Publicly Available Date: Mar 16, 2021
• Journal: Journal of Chemical Theory and Computation
• Print ISSN: 1549-9618
• Electronic ISSN: 1549-9626
• Publisher: American Chemical Society
• Peer Reviewed: Peer Reviewed
• Volume: 17
• Issue: 4
• Pages: 2137-2165
• DOI: https://doi.org/10.1021/acs.jctc.0c01269
• Keywords: Physical and Theoretical Chemistry; Computer Science Applications
• Public URL: https://nottingham-repository.worktribe.com/output/5290760
• Publisher URL: https://pubs.acs.org/doi/abs/10.1021/acs.jctc.0c01269