Date of Award
Spring 2024
Document Type
Dissertation
Degree Name
Doctor of Philosophy (PhD)
Department
Chemistry
First Advisor
Hammes-Schiffer, Sharon
Abstract
Due to their small mass, protons often exhibit non-classical behavior that can dramatically affect chemical processes. For molecular systems, nuclear quantum effects (NQEs) can be accurately described by electronic structure theory within the nuclear electronic orbital (NEO) framework, wherein select nuclei of interest are treated on the same level of ES theory as the electrons. Within the NEO framework, an affordable and systematically improvable method was developed that produces proton affinities and proton densities of the same quality as a highly accurate and expensive method. In addition to affecting ground state properties of molecules, nuclear quantum effects can also dramatically affect reactions. Larger systems such as electrode interfaces and metal-organic frameworks (MOFs) often employ proton-coupled electron transfer (PCET) reactions, wherein the quantum behavior of the transferring proton can dramatically influence reaction rates and kinetic isotope effects. In this vein, nonadiabatic PCET theory that treats the transferring proton as well as the electrons quantum mechanically was combined with periodic ES theory to identify a proton transfer coordinate that agrees with experimental benchmarks for proton discharge on Pt(111), one of the most fundamental and important electrochemical processes. In addition to electrode interfaces, PCET can occur without an applied field. Electronic structure calculations revealed a thermodynamically accessible mechanism by which a blood-stable Cu-MOF releases a vasodilator (nitric oxide) from endogenous sources, providing design principles for its application as a potent biomedical implant.
Recommended Citation
Rousseau, Benjamin John Guy, "Nuclear Quantum Effects and Proton Transfer Mechanisms in Molecular and Solid- Liquid Interface Systems" (2024). Yale Graduate School of Arts and Sciences Dissertations. 1379.
https://elischolar.library.yale.edu/gsas_dissertations/1379
