Reliable transition properties from excited-state mean-field calculations

Abstract

Delta-self-consistent field theory (delta-SCF) 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 TDDFT. 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 the simplest 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.

arXiv comment24 pages, 4 figure, 1 excel spreadsheet containing supplementary material

References in corpus (6)

• Efficient energy transfer in light-harvesting systems, I: optimal temperature, reorganization energy, and spatial-temporal correlations
• Benchmarking TD-DFT and Wave Function Methods for Oscillator Strengths and Excited-State Dipole Moments
• Excited state orbital optimization via minimizing the square of the gradient: General approach and application to singly and doubly excited states via density functional theory
• Highly Accurate Prediction of Core Spectra of Molecules at Density Functional Theory Cost: Attaining sub eV Error from a Restricted Open-Shell Kohn-Sham Approach
• Quantum transport in quantum networks and photosynthetic complexes at the steady state
• Accurate prediction of core-level spectra of radicals at density functional theory cost via square gradient minimization and recoupling of mixed configurations

Cited by in corpus (5)

• Orbital Optimized Density Functional Theory for Electronic Excited States
• Electron-Affinity Time-Dependent Density Functional Theory: Formalism and Applications to Core-Excited States
• Transition moments for STEOM-CCSD with core triples
• Variational Density Functional Calculations of Excited States: Conical Intersection and Avoided Crossing in Ethylene Bond Twisting
• Method for Calculating Excited Electronic States Using Density Functionals and Direct Orbital Optimization with Real Space Grid or Plane Wave Basis Set