Doctoral Dissertations

Abstract

"Various computational methods have been used to generate potential energy surfaces, which can help us simulate and interpret how atoms or molecules behave during a chemical reaction. For accurate work, ab initio wavefunction methods have traditionally been used, which have some disadvantages. For example, highly accurate methods scale poorly with system size (n7 or higher) and are mostly not well parallelized for calculations with multiple processors. One alternative method that has more favorable scaling with system size and is well parallelized is a computational technique called quantum Monte Carlo (QMC). QMC methods scale with the number of electrons as n3 and have been found to scale almost linearly with the number of processors, even beyond 500,000 cores. However, despite the favorable scaling towards large systems, the cost of QMC methods is relatively expensive for small systems. Small systems nevertheless make important benchmarks necessary for the new methods to gain acceptance. Thus, it was determined to study QMC methods in a few benchmark systems in order to assess its accuracy and routine applicability.

It was found that QMC methods can be very accurate comparing well with experimental measurements and other high-level ab initiomethods. Benchmark calculations with QMC produced realistic spectroscopic parameters for CO and N2. However, for small system sizes, they are relatively very expensive to perform with the cost being orders of magnitude higher than traditional methods. Consequently, their use in small systems will likely most often be restricted to only a few geometrical points of interest, unlike traditional methods. Nevertheless, deep insight into the electronic structure of a system can be obtained"--Abstract, page iv.

Advisor(s)

Dawes, Richard

Committee Member(s)

Winiarz, Jeffrey G.
Grubbs, Garry S.
Woelk, Klaus
Parris, Paul Ernest, 1954-

Department(s)

Chemistry

Degree Name

Ph. D. in Chemistry

Sponsor(s)

United States. Department of Energy
National Science Foundation (U.S.)

Comments

This research was also funded in part by National Science Foundation awards OCI-0923037 and CBET-0521602; this work was supported by the U.S. Department of Energy [grant number DESC0010616].

Publisher

Missouri University of Science and Technology

Publication Date

Summer 2017

Journal article titles appearing in thesis/dissertation

  • Photoinduced electron transfer in donor-acceptor complexes of ethylene with molecular and atomic iodine
  • Calculating potential energy curves with fixed-node diffusion Monte Carlo: CO and N2
  • Investigation of the ozone formation reaction pathway: comparisons of full configuration interaction quantum Monte Carlo and fixed-node diffusion Monte Carlo with contracted and uncontracted MRCI

Pagination

xii, 92 pages

Note about bibliography

Includes bibliographic references.

Rights

© 2017 Andrew Douglas Powell, All rights reserved.

Document Type

Dissertation - Open Access

File Type

text

Language

English

Thesis Number

T 11182

Electronic OCLC #

1003043527

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Included in

Chemistry Commons

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