Stochastic Effective Core Potentials, toward Efficient Quantum Monte Carlo Simulations of Molecules with Large Atomic Numbers

We propose a Monte Carlo method which exploits that core regions are physically independent in a molecule to almost remove their contribution to the numerical cost. The method is tantamount to computing an effective core potential on the fly, by efficiently subsampling the core regions with independent sidewalks. The removal of fluctuations in the core region enables also the dynamic in the valence region to be accelerated using a process with two time steps. As a function of the total number of electrons N he numerical overhead O ( N ) is negligible in comparison to the overall scaling O ( N 3 ) (due to the evaluation of determinants). Tests are presented on atoms, alkane chains, and clusters of silicons. We report a transferability of the parameters of the method from atoms to molecules, enabling a calibration using only single atoms. These tests display a gain in numerical efficiency between one and two orders of magnitude for large N .