Ab initio molecular dynamics via density based energy functionals

Abstract

The use of energy functionals based on charge density as the basic variable is advocated for ab initio molecular dynamics. It is demonstrated that the constraint of positivity of density can be incorporated easily by using the square root of the density for minimization of the energy functional. An ad hoc prescription for including non-local pseudopotentials for plane wave based calculations is proposed and is shown to yield improved results. Applications are reported for equilibrium geometries of small finite systems, viz. dimers and trimers of simple metal atoms like Na and Mg, which represent a rather stringent test for approximate kinetic energy functionals involved in such calculations.