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Toward Robust and Efficient Atomistic Modeling of Solvent Effects

Maldonado, Alex M. (2023) Toward Robust and Efficient Atomistic Modeling of Solvent Effects. Doctoral Dissertation, University of Pittsburgh. (Unpublished)

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Due to environmental and economic pressures, society has an ever-increasing need for renewable fuels and chemicals. Fulfilling this demand will require discovering and optimizing sustainable chemical processes. Computational screening can be used to explore chemical reactions before investing time and resources in experimental investigations. Atomistic modeling with quantum chemical methods is frequently used for gathering insight into reaction thermodynamics and kinetics. Accurate predictions of reaction pathways must account for crucial environmental effects from solvents and ions. This work investigates how to efficiently and reliably capture these effects without a priori information, such as experimental data. For example, molecular simulations with explicit solvent molecules are the most rigorous approach but bring high computational costs. Implicit solvent models are inexpensive, but their accuracy—especially for charged species or mixed solvents—is often unclear. Here, solvation schemes are discussed for mixed solvents. Implicit solvent models using only a homogeneous dielectric medium are generally inadequate, and frameworks that account for nonuniform solvent distributions are required. Then, sodium borohydride reduction of carbon dioxide is computationally investigated. This work systematically evaluates when different procedures are reliable by replacing solvent molecules from explicitly solvated structures with implicit solvent models. Implicit solvent models alone (i.e., no explicit solvent molecules) are insufficient, and the inner solvation shell is needed to model the reaction mechanism accurately. Thus, explicit solvent models are required for the reliable treatment of solvated reactions. However, the computational cost of numerous energy and force evaluations restricts their usage. Many-body gradient-domain machine learning (mbGDML) is introduced to accelerate molecular simulations based on quantum chemical data. These machine learning force fields are rapidly trained and demonstrate semi-quantitative agreement with water, acetonitrile, and methanol isomer rankings and experimental radial distribution functions.


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Item Type: University of Pittsburgh ETD
Status: Unpublished
CreatorsEmailPitt UsernameORCID
Maldonado, Alex M.amm503@pitt.eduamm5030000-0003-3280-062X
ETD Committee:
TitleMemberEmail AddressPitt UsernameORCID
Committee ChairKeith, John A.jakeith@pitt.edu0000-0002-6583-6322
Committee MemberJohnson, J. Karlkarlj@pitt.edu0000-0002-3608-8003
Committee MemberMpourmpakis, Giannisgmpourmp@pitt.edu0000-0002-3063-0607
Committee MemberJordan, Kenneth
Date: 13 June 2023
Date Type: Publication
Defense Date: 20 March 2023
Approval Date: 13 June 2023
Submission Date: 22 March 2023
Access Restriction: No restriction; Release the ETD for access worldwide immediately.
Number of Pages: 162
Institution: University of Pittsburgh
Schools and Programs: Swanson School of Engineering > Chemical Engineering
Degree: PhD - Doctor of Philosophy
Thesis Type: Doctoral Dissertation
Refereed: Yes
Uncontrolled Keywords: computational chemistry, solvents, reaction modeling, machine learning, force fields
Date Deposited: 13 Jun 2023 14:07
Last Modified: 13 Jun 2023 14:07


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