Neutral excitation density-functional theory: an efficient and variational first-principles method for simulating neutral excitations in molecules

Abstract

AbstractWe introduce neutral excitation density-functional theory (XDFT), a computationally light, generally applicable, first-principles technique for calculating neutral electronic excitations. The concept is to generalise constrained density functional theory to free it from any assumptions about the spatial confinement of electrons and holes, but to maintain all the advantages of a variational method. The task of calculating the lowest excited state of a given symmetry is thereby simplified to one of performing a simple, low-cost sequence of coupled DFT calculations. We demonstrate the efficacy of the method by calculating the lowest single-particle singlet and triplet excitation energies in the well-known Thiel molecular test set, with results which are in good agreement with linear-response time-dependent density functional theory (LR-TDDFT). Furthermore, we show that XDFT can successfully capture two-electron excitations, in principle, offering a flexible approach to target specific effects beyond state-of-the-art adiabatic-kernel LR-TDDFT. Overall the method makes optical gaps and electron-hole binding energies readily accessible at a computational cost and scaling comparable to that of standard density functional theory. Owing to its multiple qualities beneficial to high-throughput studies where the optical gap is of particular interest; namely broad applicability, low computational demand, and ease of implementation and automation, XDFT presents as a viable candidate for research within materials discovery and informatics frameworks.