Analytical Forces for the Optimized Effective Potential Calculations.

Abstract

The optimized effective potential (OEP) equation is an ill-conditioned linear system when using finite basis sets. Without any special treatment, the obtained exchange-correlation (XC) potential may have unphysical oscillations. One way to alleviate this problem is to regularize the solutions; however, a regularized XC potential is not the exact solution to the OEP equation. As a result, the system's energy is no longer variational against the Kohn-Sham (KS) potential, and the analytical forces cannot be derived from the Hellmann-Feynman theorem. In this work, we develop a robust and nearly black-box OEP method to ensure that the system's energy is variational against the KS potential. The basic idea is to add a penalty function that regularizes the XC potential to the energy functional. Analytical forces can then be derived based on the Hellmann-Feynman theorem. Another key result is that the impact of the regularization can be much reduced by regularizing the difference between the XC potential and an approximate XC potential rather than regularizing the XC potential. Numerical tests show that forces and the energy differences between systems are not sensitive to the regularization coefficient, which indicates that in practice accurate structural and electronic properties can be obtained without extrapolating the regularization coefficient to zero. We expect this new method to be found useful for calculations that employ advanced, orbital-based functionals, especially for applications that require efficient force calculations.