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Computational Elucidation of Molecular Scale Water Within Polymer Hydrates

Filonowich, Dominick S (2023) Computational Elucidation of Molecular Scale Water Within Polymer Hydrates. Master's Thesis, University of Pittsburgh. (Unpublished)

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Four polymer hydrates were investigated using multiple computational techniques, including molecular dynamics, geometry optimizations using the Kohn-Sham density functional theory Perdew–Burke-Ernzerhof (DFT PBE) exchange correlation functional, and the Local Energy Decomposition (LED) method of Neese and Bistoni. Molecular dynamics simulations on an infinitely large hydrate using universal classical forcefields did not melt, and a prototype python script to create finitely sized hydrates was developed. LED calculations quantified the degree that these polymer hydrates are formed due to electrostatic and exchange interactions between polymers chains and water molecules. In all cases, exchange interactions were approximately 1/5 the size of the electrostatic interactions, which is possible descriptor for hydrates of this type. New hypothetical hydrates were also modeled by doping oxygen into or fluoridating the PEI hemi and sesquihydrates. By calculating the binding energies of these structures, it was found that as the total binding energy decreases, the melting temperature increases. This analysis also suggested the fluoridated hydrates have may significantly weaker cohesive energies relative to that of the original hydrates, and if these structures are experimentally stable this suggests a viable means to design new hydrates for ion capture.


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Item Type: University of Pittsburgh ETD
Status: Unpublished
CreatorsEmailPitt UsernameORCID
Filonowich, Dominick Sdof13@pitt.edudof130000-0002-9519-4041
ETD Committee:
TitleMemberEmail AddressPitt UsernameORCID
Committee ChairKeith, John A.jakeith@pitt.edujakeith0000-0002-6583-6322
Committee CoChairVelankar, Sachin S.velankar@pitt.eduvelankar0000-0001-7541-1355
Committee MemberWilmer, Chris E.WILMER@pitt.eduWILMER
Date: 19 January 2023
Date Type: Publication
Defense Date: 15 July 2022
Approval Date: 19 January 2023
Submission Date: 14 November 2022
Access Restriction: 2 year -- Restrict access to University of Pittsburgh for a period of 2 years.
Number of Pages: 113
Institution: University of Pittsburgh
Schools and Programs: Swanson School of Engineering > Chemical Engineering
Degree: MS - Master of Science
Thesis Type: Master's Thesis
Refereed: Yes
Uncontrolled Keywords: Quantum Chemistry, Molecular Dynamics, Polymer Science, Clathrates, Hydrates
Date Deposited: 19 Jan 2023 19:25
Last Modified: 19 Jan 2023 19:25


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