Calculation of nonadiabatic couplings in density-functional theory

Abstract

This paper proposes methods for calculating the derivative couplings between adiabatic states in density-functional theory (DFT) and compares them with each other and with multiconfigurational self-consistent field calculations. They are shown to be accurate and, as expected, the costs of their calculation scale more favorably with system size than post-Hartree-Fock calculations. The proposed methods are based on single-particle excitations and the associated Slater transition-state densities to overcome the problem of the unavailability of multielectron states in DFT which precludes a straightforward calculation of the matrix elements of the nuclear gradient operator. An iterative scheme employing linear-response theory was found to offer the best trade-off between accuracy and efficiency. The algorithms presented here have been implemented for doublet-doublet excitations within a plane-wave-basis and pseudopotential framework but are easily generalizable to other excitations and basis sets. Owing to their fundamental importance in cases where the Born-Oppenheimer separation of motions is not valid, these derivative couplings can facilitate, for example, the treatment of nonadiabatic charge transfers, of electron-phonon couplings, and of radiationless electronic transitions in DFT.