A novel method for optimizing quantum Monte Carlo wave functions

Abstract

We propose an algorithm for optimizing quantum Monte Carlo wave functions. An improved steepest-descent technique is used, with step size automatically adjustable to obtain a procedure that converges superlinearly. We also propose a novel trial function, which has both correct electron–electron cusp conditions and correct electron–nucleus cusp conditions. To test the optimization procedure and the optimized trial function, the ground states for CH4 and H2O molecules were investigated using variational Monte Carlo (VMC) and fixed-node quantum Monte Carlo (FNQMC) calculations. For CH4 and H2O, the VMC recovered 73.3% and 57.9% of the correlation energy, respectively, and the FNQMC recovered 99.3% and 92.8%, respectively. The optimization procedure is three to five times faster than conventional usual steepest-descent procedures. The trial functions optimized are more accurate than prior trial functions of similar complexity.