Optimizing the Energy with Quantum Monte Carlo: A Lower Numerical Scaling for Jastrow–Slater Expansions

Abstract

We present an improved formalism for quantum Monte Carlo calculations of energy derivatives and properties (e.g., the interatomic forces), with a multideterminant Jastrow-Slater function. As a function of the number N_e of Slater determinants, the numerical scaling of O(N_e) per derivative we have recently reported is here lowered to O(N_e) for the entire set of derivatives. As a function of the number of electrons N, the scaling to optimize the wave function and the geometry of a molecular system is lowered to O(N³) + O(NN_e), the same as computing the energy alone in the sampling process. The scaling is demonstrated on linear polyenes up to C₆₀H₆₂ and the efficiency of the method is illustrated with the structural optimization of butadiene and octatetraene with Jastrow-Slater wave functions comprising as many as 200 000 determinants and 60 000 parameters.