Analytical energy gradient evaluation in relativistic and nonrelativistic density functional calculations.

Abstract

The expressions of analytical energy gradients in density functional theory and their implementation in programs are reported. The evaluation of analytical energy gradients can be carried out in the fully 4-component relativistic, approximate relativistic, and nonrelativistic density functional calculations under local density approximation or general gradient approximation with or without frozen core approximation using different basis sets in our programs. The translational invariance condition and the fact that the one-center terms do not contribute to the energy gradients are utilized to improve the calculation accuracy and to reduce the computational effort. The calculated results of energy gradients and optimized geometry as well as atomization energies of some molecules by the analytical gradient method are in very good agreement with results obtained by the numerical derivative method.