Reliable transition properties from excited-state mean-field calculations

Bourne Worster, Susannah; Feighan, Oliver; Manby, Frederick R.

Abstract

Delta-self-consistent field (ΔSCF) theory is a conceptually simple and computationally inexpensive method for finding excited states. Using the maximum overlap method to guide optimization of the excited state, ΔSCF has been shown to predict excitation energies with a level of accuracy that is competitive with, and sometimes better than, that of time-dependent density functional theory. Here, we benchmark ΔSCF on a larger set of molecules than has previously been considered, and, in particular, we examine the performance of ΔSCF in predicting transition dipole moments, the essential quantity for spectral intensities. A potential downfall for ΔSCF transition dipoles is origin dependence induced by the nonorthogonality of ΔSCF ground and excited states. We propose and test a simple correction for this problem, based on symmetric orthogonalization of the states, and demonstrate its use on bacteriochlorophyll structures sampled from the photosynthetic antenna in purple bacteria.

Citation

Bourne Worster, S., Feighan, O., & Manby, F. R. (2021). Reliable transition properties from excited-state mean-field calculations. The Journal of Chemical Physics, 154(12), https://doi.org/10.1063/5.0041233

• Journal Article Type: Article
• Acceptance Date: Feb 20, 2021
• Online Publication Date: Mar 22, 2021
• Publication Date: Mar 28, 2021
• Deposit Date: Jan 27, 2025
• Journal: The Journal of Chemical Physics
• Print ISSN: 0021-9606
• Electronic ISSN: 1089-7690
• Publisher: American Institute of Physics
• Peer Reviewed: Peer Reviewed
• Volume: 154
• Issue: 12
• DOI: https://doi.org/10.1063/5.0041233
• Public URL: https://durham-repository.worktribe.com/output/3353446