Wheat, Ryan M
(2021)
Computational Benchmarking and Evaluation of Transition Metal Complexes toward Materials Discovery.
Master's Thesis, University of Pittsburgh.
(Unpublished)
This is the latest version of this item.
Abstract
The synergy between computational modeling and materials analysis remains an unsolved problem, yet there is great potential for accelerating materials discovery. This work reframes the cumbersome nature of experimental intuition (trial and error) by shedding light on the utility of quantitative data as a promising alternative. With respect to Metal-Organic Frameworks, stability considerations are essential to the targeting of materials that not only possess high turnover efficiency but are also resistant to degradation. Core computational methods in this work include UFF, GFNFF, GFN2, and B97-3c for their extended utility to evaluating transition metal systems. From a molecular geometry perspective, GFN2 and B97-3c closely matched experimental bond distances for a selected series of 32 transition metal complexes (TMCs) labeled TMC32. In terms of electronic energy, bond dissociation was targeted as a means of predicting synthetic tractability and expected stability. From a separate set of 30 TMCs labeled TM30, B97-3c single-point calculations with UFF optimized geometries provided the highest accuracy. A subset of the tmQM dataset, focused solely on complexes with Ni-Cl bonds, supported the argument that GFN2 is infeasible for calculating electronic effects in its current state. These studies elevate B97-3c as an efficient method that can accelerate efforts to quantify stability in TMCs, with future work focused on correlating this data to improve MOF modeling capabilities towards materials discovery.
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Details
| Item Type: |
University of Pittsburgh ETD
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| Status: |
Unpublished |
| Creators/Authors: |
|
| ETD Committee: |
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| Date: |
3 May 2021 |
| Date Type: |
Publication |
| Defense Date: |
30 March 2021 |
| Approval Date: |
3 May 2021 |
| Submission Date: |
7 April 2021 |
| Access Restriction: |
No restriction; Release the ETD for access worldwide immediately. |
| Number of Pages: |
29 |
| Institution: |
University of Pittsburgh |
| Schools and Programs: |
Dietrich School of Arts and Sciences > Chemistry |
| Degree: |
MS - Master of Science |
| Thesis Type: |
Master's Thesis |
| Refereed: |
Yes |
| Uncontrolled Keywords: |
MOF, DFT, GFN, Enthalpy, Bond, Metal, Organic |
| Date Deposited: |
03 May 2021 15:37 |
| Last Modified: |
03 May 2021 15:37 |
| URI: |
http://d-scholarship.pitt.edu/id/eprint/40547 |
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Computational Benchmarking and Evaluation of Transition Metal Complexes toward Materials Discovery. (deposited 03 May 2021 15:37)
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