Quantum Monte Carlo with variable spins: fixed-phase and fixed-node approximations

Abstract: We study several aspects of the recently introduced fixed-phase spin-orbit diffusion Monte Carlo (FPSODMC) method, in particular, its relation to the fixed-node method and its potential use as a general approach for electronic structure calculations. We illustrate constructions of spinor-based wave functions with the full space-spin symmetry without assigning up or down spin labels to particular electrons, effectively "complexifying" even ordinary real-valued wave functions. Interestingly, with proper choice of the simulation parameters and spin variables, such fixed-phase calculations enable one to reach also the fixed-node limit. The fixed-phase solution provides a straightforward interpretation as the lowest bosonic state in a given effective potential generated by the many-body approximate phase. In addition, the divergences present at real wave function nodes are smoothed out to lower dimensionality, decreasing thus the variation of sampled quantities and making the sampling also more straightforward. We illustrate some of these properties on calculations of selected first-row systems that recover the fixed-node results with quantitatively similar levels of the corresponding biases. At the same time, the fixed-phase approach opens new possibilities for more general trial wave functions with further opportunities for increasing accuracy in practical calculations.