Solving Schroedinger's equation using random walks

Exact and almost exact solutions for energies and properties of atoms and molecules can be obtained by quantum Monte Carlo (QMC) methods. This thesis is composed of different contributions to various QMC methodologies, as well as applications to electronic excitations of biological systems.;We propose a wave function optimization functional that is robust regarding the presence of outliers. Our work, and subsequent applications by others, has shown the convergence properties and robustness of the absolute deviation (AD) functional as compared to the variance functional (VF). We apply the method to atoms from the second row of the periodic table, as well as third-row transition metal atoms, including an all-electron calculation of Sc. In all cases, the AD functional converges faster than the VF.;Soft effective core potentials (ECPs) with no divergence at the origin are constructed and validated for second- an third-row atoms of the periodic table. The ECPs we developed have been used by others in several successful studies.;As an application of the DMC approach to biochemical problems, we studied the electronic excitations of free-base porphyrin and obtained results in excellent agreement with experiment. These findings validate the use of the DMC approach for these kinds of systems.;A study of the role of spheroidene in the photo-protection mechanism of Rhodobacter sphaeroides is described. At the time of writing, calculations for the estimation of excitation energies for the bacteriochlorophyll and spheroidene molecules as well as storage of the random walkers for future prediction of the excitation energy transfer rate are being performed.;To date, the calculations mentioned above are the largest all-electron studies on molecules. For the computation of these systems, a sparse linear-scaling DMC algorithm was developed. This algorithm provides a speedup of at least a factor of ten over previously published methods. The method is validated on systems up to 390 electrons.;A summary of the Fermion Monte Carlo (FMC) algorithm as well as an application to the Be atom are discussed.;The Zori package, a linear-scaling massively-parallel open-source program that uses modern programming libraries, was developed. The program is made available to the public under the GNU/General Public License (GPL). The capabilities of the Zori program are summarized.