Reliable transition properties from excited-state mean-field calculations

Delta-self-consistent field (Delta SCF) 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, Delta SCF 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 Delta SCF on a larger set of molecules than has previously been considered, and, in particular, we examine the performance of Delta SCF in predicting transition dipole moments, the essential quantity for spectral intensities. A potential downfall for Delta SCF transition dipoles is origin dependence induced by the nonorthogonality of Delta 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.

Automated summary

Delta SCF theory is a conceptually simple and computationally inexpensive method for finding excited states with competitive accuracy. However, a potential issue with Delta SCF transition dipoles is origin dependence induced by nonorthogonality of ground and excited states, which can be corrected by symmetric orthogonalization.