Practical Schemes for Accurate Forces in Quantum Monte Carlo

While the computation of interatomic forces has become a well-established practice within variational Monte Carlo (VMC), the use of the more accurate Fixed-Node Diffusion Monte Carlo (DMC) method is still largely limited to the computation of total energies on structures obtained at a lower level of theory. Algorithms to compute exact DMC forces have been proposed in the past, and one such scheme is also put forward in this work, but remain rather impractical due to their high computational cost. As a practical route to DMC forces, we therefore revisit here an approximate method, originally developed in the context of correlated sampling and named here the Variational Drift-Diffusion (VD) approach. We thoroughly investigate its accuracy by checking the consistency between the approximate VD force and the derivative of the DMC potential energy surface for the SiH and C2 molecules and employ a wide range of wave functions optimized in VMC to assess its robustness against the choice of trial function. We find that, for all but the poorest wave function, the discrepancy between force and energy is very small over all interatomic distances, affecting the equilibrium bond length obtained with the VD forces by less than 0.004 au. Furthermore, when the VMC forces are approximate due to the use of a partially optimized wave function, the DMC forces have smaller errors and always lead to an equilibrium distance in better agreement with the experimental value. We also show that the cost of computing the VD forces is only slightly larger than the cost of calculating the DMC energy. Therefore, the VD approximation represents a robust and efficient approach to compute accurate DMC forces, superior to the VMC counterparts.