Self-Consistent Field Methods for Excited States in Strong Magnetic Fields: A Comparison Between Energy- and Variance-based Approaches

David, Grégoire; Irons, Tom J.P.; Fouda, Adam E.A.; Furness, James W.; Teale, Andrew M.

Abstract

Self-consistent field methods for excited states offer an attractive low-cost route to study not only excitation energies but also properties of excited states. Here, we present the generalization of two self-consistent field methods, the maximum overlap method (MOM) and the σ-SCF method, to calculate excited states in strong magnetic fields and investigate their stability and accuracy in this context. These methods use different strategies to overcome the well-known variational collapse of energy-based optimizations to the lowest solution of a given symmetry. The MOM tackles this problem in the definition of the orbital occupations to constrain the self-consistent field procedure to converge on excited states, while the σ-SCF method is based on the minimization of the variance instead of the energy. To overcome the high computational cost of the variance minimization, we present a new implementation of the σ-SCF method with the resolution of identity approximation, allowing the use of large basis sets, which is an important requirement for calculations in strong magnetic fields. The accuracy of these methods is assessed by comparison with the benchmark literature data for He, H2, and CH+. The results reveal severe limitations of the variance-based scheme, which become more acute in large basis sets. In particular, many states are not accessible using variance optimization. Detailed analysis shows that this is a general feature of variance optimization approaches due to the masking of local minima in the optimization. In contrast, the MOM shows promising performance for computing excited states under these conditions, yielding results consistent with available benchmark data for a diverse range of electronic states.

Citation

David, G., Irons, T. J., Fouda, A. E., Furness, J. W., & Teale, A. M. (2021). Self-Consistent Field Methods for Excited States in Strong Magnetic Fields: A Comparison Between Energy- and Variance-based Approaches. Journal of Chemical Theory and Computation, 17(9), 5492-5508. https://doi.org/10.1021/acs.jctc.1c00236

• Journal Article Type: Article
• Acceptance Date: Jul 8, 2021
• Online Publication Date: Aug 16, 2021
• Publication Date: Sep 14, 2021
• Deposit Date: Jul 19, 2021
• Publicly Available Date: Aug 17, 2022
• Journal: Journal of Chemical Theory and Computation
• Print ISSN: 1549-9618
• Electronic ISSN: 1549-9626
• Peer Reviewed: Peer Reviewed
• Volume: 17
• Issue: 9
• Pages: 5492-5508
• DOI: https://doi.org/10.1021/acs.jctc.1c00236
• Keywords: Physical and Theoretical Chemistry; Computer Science Applications
• Public URL: https://nottingham-repository.worktribe.com/output/5806105
• Publisher URL: https://pubs.acs.org/doi/full/10.1021/acs.jctc.1c00236#