Reliable transition properties from excited-state mean-field calculations

Susannah L Bourne-Worster, Oliver J H Feighan, Frederick R Manby*

*Corresponding author for this work

Research output: Contribution to journalArticle (Academic Journal)peer-review

1 Citation (Scopus)
23 Downloads (Pure)

Abstract

Delta-self-consistent field theory (∆SCF) is a conceptually simple and computationally in- expensive method for finding excited states. Using the maximum overlap method to guide optimization of the excited state, ∆SCF has been shown to predict excitation energies with a level of accuracy that is competitive with, and sometimes better than, that of TDDFT. Here we benchmark ∆SCF on a larger set of molecules than has previously been considered, and, in particular, we examine the performance of ∆SCF in predicting transition dipole moments, the essential quantity for spectral intensities. A potential downfall for ∆SCF transition dipoles is origin dependence induced by the nonorthogonality of ∆SCF 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.
Original languageEnglish
Article number124106
JournalThe Journal of Chemical Physics
Volume154
Issue number12
DOIs
Publication statusPublished - 22 Mar 2021

Bibliographical note

Funding Information:
We gratefully acknowledge the funding agencies that supported this work: O.F. was funded by the U.S. Department of Energy (Grant No. DE-FOA-0001912). S.B.W. was supported by a research fellowship from the Royal Commission for the Exhibition of 1851. We are grateful for a comment from Diptarka Hait pointing out that the transition dipole can alternatively be evaluated by aligning the molecular center of charge with the origin. F.R.M. is the co-founder and CTO of Entos, Inc. The other authors declare no conflict of interest.

Publisher Copyright:
© 2021 Author(s).

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