Gasperich, Kevin E.
(2020)
Calculation of Intermolecular Interactions via Diffusion Monte Carlo.
Doctoral Dissertation, University of Pittsburgh.
(Unpublished)
This is the latest version of this item.
Abstract
Quantum chemistry is a useful tool that provides insight into the properties and behavior of chemical systems.
Modern software packages have made quantum chemistry methods more easily accessible, and the continued increase in available computational resources has allowed them to be applied to larger systems at higher levels of theory.
Two significant problems that the field faces are the high computational complexity of high-level methods and the shift toward parallelism in high performance computing architectures.
This work examines the treatment of weakly interacting molecular systems with the fixed-node diffusion Monte Carlo (DMC) method.
DMC and other quantum Monte Carlo (QMC) methods offer a possible solution to both of the aforementioned problems: they can produce near-exact results with a lower scaling (with respect to problem size) than other similarly-accurate methods, and they are inherently parallel, so there is little additional cost associated with distributing the work of a single QMC calculation across a large number of processing units.
The only error in DMC that is not systematically improvable is the constraint of a fixed nodal surface of the many-particle wave function of the system being studied.
There are many cases in which a single Slater determinant trial function is sufficient to obtain accurate results, but there are others in which more sophisticated multi-determinant trial functions are necessary.
Furthermore, it is non-trivial to generate nodal surfaces of similar quality for isolated and interacting molecules, so cancellation of errors is not guaranteed.
We examine the use of different single- and multi-determinant trial functions in DMC calculations on small chemical systems with the goal of further understanding how to construct appropriate trial functions for molecules and clusters.
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Details
| Item Type: |
University of Pittsburgh ETD
|
| Status: |
Unpublished |
| Creators/Authors: |
|
| ETD Committee: |
|
| Date: |
16 January 2020 |
| Date Type: |
Publication |
| Defense Date: |
25 October 2019 |
| Approval Date: |
16 January 2020 |
| Submission Date: |
21 October 2019 |
| Access Restriction: |
No restriction; Release the ETD for access worldwide immediately. |
| Number of Pages: |
183 |
| Institution: |
University of Pittsburgh |
| Schools and Programs: |
Dietrich School of Arts and Sciences > Chemistry |
| Degree: |
PhD - Doctor of Philosophy |
| Thesis Type: |
Doctoral Dissertation |
| Refereed: |
Yes |
| Uncontrolled Keywords: |
electronic structure, intermolecular interactions, computational chemistry |
| Date Deposited: |
16 Jan 2020 18:33 |
| Last Modified: |
16 Jan 2020 18:33 |
| URI: |
http://d-scholarship.pitt.edu/id/eprint/37941 |
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