Orbital Optimized Density Functional Theory for Electronic Excited States

Abstract

Density functional theory (DFT) based modeling of electronic excited states is of importance for investigation of the photophysical/photochemical properties and spectroscopic characterization of large systems. The widely used linear response time-dependent DFT (TDDFT) approach is however not effective at modeling many types of excited states, including (but not limited to) charge-transfer states, doubly excited states and core-level excitations. In this perspective, we discuss state-specific orbital optimized (OO) DFT approaches as an alterative to TDDFT for electronic excited states. We motivate the use of OO-DFT methods and discuss reasons behind their relatively restricted historical usage (vs TDDFT). We subsequently highlight modern developments that address these factors and allow efficient and reliable OO-DFT computations. Several successful applications of OO-DFT for challenging electronic excitations are also presented, indicating their practical efficacy. OO-DFT approaches are thus increasingly becoming a useful route for computing excited states of large chemical systems. We conclude by discussing the limitations and challenges still facing OO-DFT methods, as well as some potential avenues for addressing them.

References in corpus (4)

• 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
• Accurate prediction of core-level spectra of radicals at density functional theory cost via square gradient minimization and recoupling of mixed configurations
• Reliable transition properties from excited-state mean-field calculations
• Self-consistent Møller-Plesset Perturbation Theory For Excited States

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