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 $O(N^3)+O(N N_e)$, the same as computing the energy alone in the sampling process. The scaling is demonstrated on linear polyenes up to C${60}$H${62}$ 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 200000 determinants and 60000 parameters.