We present a direct generalization of the ground state density functional theory (DFT) to describe electronically singly excited states. This method is built upon the recently developed excited state variational principle and the excited state mean-field platform. As in the ground<br/>state DFT, a fictitious, non-interacting system is applied to compute the kinetic energy of the excited states. Additional correlation energy that arises due to the multi-reference nature of the fictitious system is manually added to account for spin symmetry and static correlation effect. By allowing the charge density of the excited states to relax according to the excitation, we are able to go beyond the adiabatic approximation made by the time-dependent density functional theory (TDDFT). In charge-transfer excited states where adiabatic approximation produces substantial amount of errors, our method yields accurate predictions to both the excitation energy values and their asymptotic behaviors, surpassing the accuracy of the range-separated hybrid functionals.

New excited state density functional theory for single excitations

2019 Fall National Meeting

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