Accelerating Convergence in Fock Space Quantum Monte Carlo Methods.

Abstract

The convergence of full configuration interaction quantum Monte Carlo (FCIQMC) is accelerated using a quasi-Newton propagation (QN) which can also be applied to coupled cluster Monte Carlo (CCMC). The computational scaling of this optimized propagation is [Formula: see text], keeping the additional computational cost to a bare minimum. Its effects are investigated deterministically and stochastically on a model system, the uniform electron gas, with Hilbert space size up to 1040, and shown to accelerate convergence of the instantaneous projected energy by over an order of magnitude in the FCIQMC test case. Its capabilities are then demonstrated with FCIQMC on an archetypical quantum chemistry problem, the chromium dimer, in an all-electron basis set with Hilbert space size of about 1022 yielding highly accurate FCI energies.