jz9b00712_si_001.pdf (246.74 kB)
Excited-State Potential Energy Surfaces, Conical Intersections, and Analytical Gradients from Ground-State Density Functional Theory
journal contribution
posted on 2019-04-30, 00:00 authored by Yuncai Mei, Weitao YangKohn–Sham
density functional theory (KS-DFT) has been a
well-established theoretical foundation for ground-state electronic
structure and has achieved great success in practical calculations.
Recently, utilizing the eigenvalues from KS or generalized KS (GKS)
calculations as an approximation to the quasiparticle energies, our
group demonstrated a method to calculate the excitation energies from
(G)KS calculation on the ground-state (N –
1)-electron system. This method is now called QE-DFT (quasiparticle
energies from DFT). In this work, we extend this QE-DFT method to
describe excited-state potential energy surfaces (PESs), conical intersections,
and the analytical gradients of excited-state PESs. The analytical
gradients were applied to perform geometry optimization for excited
states. In conjunction with several commonly used density functional
approximations, QE-DFT can yield PESs in the vicinity of the equilibrium
structure with accuracy similar to that from time-dependent DFT (TD-DFT).
Furthermore, it describes conical intersection well, in contrast to
TD-DFT. Good results for geometry optimization, especially bond length,
of low-lying excitations for 14 small molecules are presented. The
capability of describing excited-state PESs, conical intersections,
and analytical gradients from QE-DFT and its efficiency based on just
ground-state DFT calculations should be of great interest for describing
photochemical and photophysical processes in complex systems.