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Insights into Chemical Reactions at Interfaces from Enhanced Sampling and Global Optimization Algorithms.

Record Type:	Electronic resources : Monograph/item
Title/Author:	Insights into Chemical Reactions at Interfaces from Enhanced Sampling and Global Optimization Algorithms./
Author:	Ludwig, Thomas.
Published:	Ann Arbor : ProQuest Dissertations & Theses, : 2021,
Description:	185 p.
Notes:	Source: Dissertations Abstracts International, Volume: 83-03, Section: B.
Contained By:	Dissertations Abstracts International83-03B.
Subject:	Quantum physics. -
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=28671160
ISBN:	9798538198849

Insights into Chemical Reactions at Interfaces from Enhanced Sampling and Global Optimization Algorithms.
Ludwig, Thomas.

Insights into Chemical Reactions at Interfaces from Enhanced Sampling and Global Optimization Algorithms. - Ann Arbor : ProQuest Dissertations & Theses, 2021 - 185 p.

Source: Dissertations Abstracts International, Volume: 83-03, Section: B.

Thesis (Ph.D.)--Stanford University, 2021.

This item must not be sold to any third party vendors.

Many important technologies and current scientific challenges involve chemical reactions that occur in complex environments, such as surfaces/interfaces or condensed phases which have complex structures and dynamics under reaction conditions. Engineering catalysts and processes for these reactions depends on developing an understanding of the mechanisms that determine the rates of these reactions. Applying computational modeling to catalytic reactions is challenging for several reasons; my work demonstrates several strategies for modeling increasingly complex chemical reactions.Accurate theoretical study of catalytic interfaces and solvent effects has been an active area of research for decades, as it requires simultaneously including detailed electronic structure and chemisorption effects from the catalyst and the many intermolecular interactions and long-range electrostatic interactions from the solvent, electrolyte or other surrounding environment, all of which must be sampled over an ensemble of configurations. I address this challenge by systematically applying global optimization algorithms to models of solvent-metal interfaces. I explain trends in adsorbate-electrolyte interactions and relate these to the adsorbate dipole moment and hydrogen bonding affinity, and shed new light on models of ion promotion effects. And I extend these methods to study the interfaces of nonaqueous solvents with transition metals, uncovering several new insights into the effects of solvent chemisorption on a variety of metal surfaces.The effect of temperature on the reaction free energies and barriers of elementary chemical reactions on surfaces is often calculated using the harmonic approximation. This is due to the computational expense of first principles calculations and the simplicity of the harmonic approximation. Often these methods rely on system-specific intuition and assumptions regarding which configurations and types of anharmonicities may be important. More rigorous, scalable and efficient free energy and enhanced sampling methods would be useful in addressing this challenge. In this thesis I describe applying a state-of-the art machine learning based enhanced sampling method to a density functional theory (DFT) model of a prototypical surface reaction. This method calculates the free energy profile of the reaction more efficiently (fewer calculations required) than other currently widely used free energy methods, while exploring and identifying the critical states in the reaction mechanism. I also apply metadyamics to study nitrogen dissociation in lithium, demonstrating the use of an enhanced sampling algorithm for the exploration of reaction mechanisms and calculation of rate constants of a surface reaction. This work is a step toward systematic, generalizable methods for the computational study of chemical reactions in complex environments.

ISBN: 9798538198849Subjects--Topical Terms:

726746
Quantum physics.

Insights into Chemical Reactions at Interfaces from Enhanced Sampling and Global Optimization Algorithms.
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506 $a This item must not be sold to any third party vendors.
520 $a Many important technologies and current scientific challenges involve chemical reactions that occur in complex environments, such as surfaces/interfaces or condensed phases which have complex structures and dynamics under reaction conditions. Engineering catalysts and processes for these reactions depends on developing an understanding of the mechanisms that determine the rates of these reactions. Applying computational modeling to catalytic reactions is challenging for several reasons; my work demonstrates several strategies for modeling increasingly complex chemical reactions.Accurate theoretical study of catalytic interfaces and solvent effects has been an active area of research for decades, as it requires simultaneously including detailed electronic structure and chemisorption effects from the catalyst and the many intermolecular interactions and long-range electrostatic interactions from the solvent, electrolyte or other surrounding environment, all of which must be sampled over an ensemble of configurations. I address this challenge by systematically applying global optimization algorithms to models of solvent-metal interfaces. I explain trends in adsorbate-electrolyte interactions and relate these to the adsorbate dipole moment and hydrogen bonding affinity, and shed new light on models of ion promotion effects. And I extend these methods to study the interfaces of nonaqueous solvents with transition metals, uncovering several new insights into the effects of solvent chemisorption on a variety of metal surfaces.The effect of temperature on the reaction free energies and barriers of elementary chemical reactions on surfaces is often calculated using the harmonic approximation. This is due to the computational expense of first principles calculations and the simplicity of the harmonic approximation. Often these methods rely on system-specific intuition and assumptions regarding which configurations and types of anharmonicities may be important. More rigorous, scalable and efficient free energy and enhanced sampling methods would be useful in addressing this challenge. In this thesis I describe applying a state-of-the art machine learning based enhanced sampling method to a density functional theory (DFT) model of a prototypical surface reaction. This method calculates the free energy profile of the reaction more efficiently (fewer calculations required) than other currently widely used free energy methods, while exploring and identifying the critical states in the reaction mechanism. I also apply metadyamics to study nitrogen dissociation in lithium, demonstrating the use of an enhanced sampling algorithm for the exploration of reaction mechanisms and calculation of rate constants of a surface reaction. This work is a step toward systematic, generalizable methods for the computational study of chemical reactions in complex environments.
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