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Title: A novel quantum Monte Carlo method for molecular systems
Author: Booth, G. H.
Awarding Body: University of Cambridge
Current Institution: University of Cambridge
Date of Award: 2010
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This thesis is concerned with the development of a new ab initio Monte Carlo method for the evaluation of exact, basis set correlation energies. A simple set of rules acting on signed walkers allow for the simulation of the underlying imaginary-time Schrödinger equation in a finite space of Slater determinants. These rules return probabilistic events which are stochastically realised in each step of the algorithm. The antisymmetric space in which the dynamic operates precludes the emergence of Bosonic solutions, and the Fermion sign problem is countered without approximation by inclusion of annihilation events between walkers of different sign. The method is applied to many molecular systems described by common Gaussian basis sets. Single point calculations, binding curves, basis set expansions and detailed studies of ionisation potentials are included. In these investigations, the method is compared to several alternative quantum chemical methods as well as exact full configuration interaction results to asses its qualities. The method is found to significantly reduce the memory and CPU requirements compared to exact diagonalisation methods, and includes an effective parallelisation scheme which scales almost linearly up to thousands of processors. This extends the scope of exact multireference calculations and allows for larger systems than previously possible to be treated.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available