Multicomponent Density-Functional Theory

Abstract

The coupling between electronic and nuclear motion plays an essential role in a wide range of physical phenomena. A few important research fields in which this is the case are superconductivity in solids, quantum transport where one needs to take into account couplings between electrons and phonons, the polaronic motion in polymer chains, and the ionization-dissociation dynamics of molecules in strong laser fields. Our goal is to set up a time-dependent multicomponent density-functional theory (TDMCDFT) to provide a general framework to describe these diverse phenomena. In TDMCDFT the electrons and nuclei are treated completely quantum mechanically from the outset. The basic variables of the theory are the electron density n, which will be defined in a body-fixed frame attached to the nuclear framework, and the diagonal of the nuclear N-body density matrix Γ, which will depend on all the nuclear coordinates. The chapter is organized as follows: We start out by defining the coordinate transformations to obtain a suitable Hamiltonian for defining our densities to be used as basic variables in the theory. We then discuss the basic one-to-one correspondence between TD potentials and TD densities, and subsequently, the resulting TD Kohn-Sham equations, the action functional, and linear response theory. As an example we discuss a diatomic molecule in a strong laser field.