Gradient Descent Optimization of Fermion Nodes in Diffusion Monte Carlo

TL;DR

This paper introduces a novel stochastic gradient descent method to optimize fermion nodes directly within diffusion Monte Carlo, significantly improving the accuracy of ground-state energy calculations for atomic and molecular systems.

Contribution

It develops a new PGD-based approach for directly optimizing fermion nodes in DMC, bypassing traditional non-DMC methods and achieving improved energy results.

Findings

Nodes optimized by the method match DMC energies of variational Monte Carlo.

The approach effectively improves trial wavefunction nodes for atoms and molecules.

The method maintains the cusp condition during optimization.

Abstract

We present a method for optimizing the location of the fermion ground-state nodes using a combination of diffusion Monte Carlo (DMC) and projected gradient descent (PGD). A PGD iteration shifts the parameters of an arbitrary node-fixing trial function in the opposite direction of the DMC energy gradient, while maintaining the cusp condition for atomic electrons. The energy gradient is calculated from DMC walker distributions by one of three methods we derive from an exact analytical expression. We combine our energy gradient calculation methods with different gradient descent algorithms and a projection operator that maintains the cusp condition. We apply this stochastic PGD method to trial functions of Be, Li$_2$, and Ne, all consisting of a single Slater determinant with randomized parameters, and find that the nodes dramatically improve to the same DMC energy as nodes optimized by variational Monte Carlo. Our method, therefore, departs from the standard procedure of optimizing the nodes with a non-DMC scheme such as variational Monte Carlo, Density function theory, or configuration interaction based calculation, which do not directly minimize the DMC energy.