The quantum Monte Carlo (QMC) is one of the most promising many-body electronic structure approaches. It employs stochastic techniques for solving the stationary Schr\" odinger equation and for evaluation of expectation values. The key advantage of QMC is its capability to use the explicitly correlated wave functions, which allow the study of many-body effects beyond the reach of mean-field methods. The most important limit on QMC accuracy is the fixed-node approximation, which comes from necessity to circumvent the fermion sign problem. The size of resulting fixed-node errors depends on the quality of the nodes (the subset of position space where the wave function vanishes) of a used wave function. In this dissertation, we analyze the nodal properties of the existing fermionic wave functions and offer new types of variational wave functions with improved nodal structure.
We study nodes of fermionic ground state wave functions. For two dimensions and higher we prove that spin-polarized, noninteracting fermions in a harmonic well have two nodal cells for arbitrary system size. The result extends to noninteracting or mean-field models in other geometries and to Hartree-Fock atomic states. Spin-unpolarized noninteracting states have multiple nodal cells; however, interactions and many-body correlations generally relax the multiple cells to the minimal number of two. With some conditions, this is proved for interacting two and higher dimensions harmonic fermion systems of arbitrary size using the Bardeen-Cooper-Schrieffer variational wave function.