Understanding ground and excited-state molecular structure in strong magnetic fields using the maximum overlap method

Wibowo, Meilani; Huynh, Bang C.; Cheng, Chi Y.; Irons, Tom J. P.; Teale, Andrew M.

Abstract

The maximum overlap method (MOM) provides a simple but powerful approach for performing calculations on excited states by targeting solutions with non-Aufbau occupations from a reference set of molecular orbitals. In this work, the MOM is used to access excited states of (Formula presented.) and (Formula presented.) in strong magnetic fields. The lowest (Formula presented.), (Formula presented.) and (Formula presented.) states of (Formula presented.) in the absence of a field are compared with the corresponding states in strong magnetic fields. The changes in molecular structure in the presence of the field are examined by performing excited state geometry optimisations using the MOM. The (Formula presented.) state is significantly stabilised by the field, becoming the ground state in strong fields with a preferred orientation perpendicular to the applied field. Its potential energy surface evolves from being repulsive to bound, with an equilateral equilibrium geometry. In contrast, the (Formula presented.) state is destabilised and its structure distorts to an isosceles form with the longest H−H bond parallel to the applied field. Comparisons are made with the (Formula presented.) state of H3, which also becomes bound with an equilateral geometry at high fields. The structures of the high-spin ground states are rationalised by orbital correlation diagrams constructed using constrained geometry optimisations.

Citation

Wibowo, M., Huynh, B. C., Cheng, C. Y., Irons, T. J. P., & Teale, A. M. (2022). Understanding ground and excited-state molecular structure in strong magnetic fields using the maximum overlap method. Molecular Physics, Article e2152748. https://doi.org/10.1080/00268976.2022.2152748

• Journal Article Type: Article
• Acceptance Date: Nov 4, 2022
• Online Publication Date: Dec 13, 2022
• Publication Date: Dec 13, 2022
• Deposit Date: Dec 19, 2022
• Publicly Available Date: Jan 6, 2023
• Journal: Molecular Physics
• Print ISSN: 0026-8976
• Electronic ISSN: 1362-3028
• Publisher: Informa UK Limited
• Peer Reviewed: Peer Reviewed
• Article Number: e2152748
• DOI: https://doi.org/10.1080/00268976.2022.2152748
• Keywords: Physical and Theoretical Chemistry; Condensed Matter Physics; Molecular Biology; Biophysics
• Public URL: https://nottingham-repository.worktribe.com/output/14894792
• Publisher URL: https://www.tandfonline.com/doi/full/10.1080/00268976.2022.2152748