Non-adiabatic electron dynamics in time-dependent density-functional theory

Abstract

Time-dependent density-functional theory (TDDFT) treats dynamical exchange and correlation (xc) via a single-particle potential, Vxc(r,t), defined as a nonlocal functional of the density n(r',t'). The popular adiabatic local-density approximation (ALDA) for Vxc(r,t) uses only densities at the same space-time point (r,t). To go beyond the ALDA, two local approximations have been proposed based on quantum hydrodynamics and elasticity theory: (a) using the current as basic variable (C-TDDFT) [G. Vignale, C. A. Ullrich, and S. Conti, Phys. Rev. Lett. 79, 4878 (1997)], (b) working in a co-moving Lagrangian reference frame (L-TDDFT) [I. V. Tokatly, Phys. Rev. B 71, 165105 (2005)]. This paper illustrates, compares, and analyzes both non-adiabatic theories for simple time-dependent model densities in the linear and nonlinear regime, for a broad range of time and frequency scales. C- and L-TDDFT are identical in certain limits, but in general exhibit qualitative and quantitative differences in their respective treatment of elastic and dissipative electron dynamics. In situations where the electronic density rapidly undergoes large deformations, it is found that non-adiabatic effects can become significant, causing the ALDA to break down.