IMPLEMENTATION OF GRADIENT-CORRECTED EXCHANGE-CORRELATION POTENTIALS IN CAR-PARRINELLO TOTAL-ENERGY CALCULATIONS

The application of gradient-corrected exchange-correlation functionals in total-energy calculations using a plane-wave basis set is discussed. The usual form of the exchange-correlation potential includes gradients whose calculation requires the use of a high-quality representation of the density which is computationally expensive in both memory and time. These problems may be overcome by defining an exchange-correlation potential for the discrete set of grid points consistent with the discretized form of the exchange-correlation energy that is used in Car-Parrinello-type total-energy calculations. This potential can be calculated exactly on the minimum fast-Fourier-transform grid and gives improved convergence and stability as well as computational efficiency.