Real-time time-dependent self-consistent field methods with dynamic magnetic fields

• Published in: The Journal of chemical physics 2023-09, Vol.159 (10)
• Main Authors: Wibowo-Teale, Meilani, Ennifer, Benjamin J., Wibowo-Teale, Andrew M.
• Format: Article
• Language: English
• Subjects: Autocorrelation functions; Benchmarks; Electron density; Electrons; Fourier transforms; Hydrogen atoms; Magnetic fields; Mathematical analysis; Real time; Self consistent fields; Symmetry; Time dependence
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/5.0160317

The first finite basis set implementation of the real-time time-dependent self-consistent field method in a dynamic (time-dependent) magnetic field using London atomic orbitals (LAOs) is presented. The accuracy of the finite basis approach using LAOs is benchmarked against numerical results from the literature for the hydrogen atom and H2 in the presence of rapidly oscillating magnetic fields. This comparison is used to inform the choice of appropriate basis sets for studies under such conditions. Remarkably, relatively modest compact LAO basis sets are sufficient to obtain accurate results. Analysis of electron dynamics in the hydrogen atom shows that LAO calculations correctly capture the time evolution of orbital occupations. The Fourier transformation of the autocorrelation function yields a power spectrum exhibiting harmonics associated with coherent emission, which closely matches the literature and further confirms the accuracy of this approach. The dynamical response of the electron density in H2 for a magnetic field parallel to the internuclear axis shows similar behavior to benchmark studies. The flexibility of this implementation is then demonstrated by considering how the dynamical response changes as a function of the orientation of the molecule relative to the applied field. At non-parallel orientations, the symmetry of the system is lowered and numerical benchmark data, which exploit cylindrical symmetry, are no-longer readily available. The present study demonstrates the utility of LAO-based calculations for extreme dynamic magnetic fields, providing a stress-test on the choice of basis. Future applications of this approach for less extreme dynamic magnetic fields are briefly discussed.