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Advances in deterministic, stochastic, and semistochastic quantum chemistry

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Holmes_cornellgrad_0058F_10020.pdf (946.15 KB)
Permanent Link(s)
https://doi.org/10.7298/X4GH9FXP
https://hdl.handle.net/1813/47777
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Cornell Theses and Dissertations
Author
Holmes, Adam
Abstract

In this dissertation, I present my original research in the development of algorithms for computing ground-state properties of strongly-correlated electronic systems from first principles. I present three main algorithms. First, I present a 'semistochastic' projection algorithm, dubbed Semistochastic Quantum Monte Carlo, which combines the best qualities of deterministic and stochastic methods for projecting out a ground state wavefunction in a basis of Slater determinants. This new algorithm can treat systems as large as a fully-stochastic algorithm can, while dramatically reducing the statistical uncertainty and bias by treating the most important part of the problem deterministically. Second, I present an efficient algorithm for sampling many-particle states in Fock space with probability proportional to the Hamiltonian matrix element connecting them to a reference state, which I refer to as the heat-bath distribution. This sampling algorithm, referred to as Efficient Heat-bath Sampling in Fock Space, factors and approximates the heat-bath probabilities in such a way that they can be efficiently stored and sampled, without having to enumerate all of the possible excitations. Efficient Heat-bath Sampling dramatically improves the efficiency of stochastic Fock space methods by sampling the more relevant Slater determinants more frequently. Third, I present the deterministic analog of Efficient Heat-bath Sampling, which enables one to generate all Slater determinants that are connected to a reference by Hamiltonian matrix elements larger in magnitude than a cutoff, without wasting any time on those determinants that do not meet the cutoff. This deterministic heat-bath \sampling" algorithm is then incorporated into a highly-efficient quantum chemistry algorithm that I call Heat-bath Configuration Interaction, which rst generates a variational wavefunction and then computes the lowest-order perturbative correction. Both the variational and perturbative stages of Heat-bath Configuration Interaction make use of deterministic heat-bath "sampling" to perform highly efficient calculations using only the most important Slater determinants.

Date Issued
2017-01-30
Keywords
Computer science
•
electronic structure theory
•
quantum Monte Carlo
•
strongly-correlated electrons
•
Quantum physics
•
Molecular chemistry
Committee Chair
Umrigar, Cyrus Jehangir
Committee Member
Mueller, Erich
Franck, Carl Peter
Degree Discipline
Physics
Degree Name
Ph. D., Physics
Degree Level
Doctor of Philosophy
Type
dissertation or thesis

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