Computational modeling of environmentally relevant reactions

Loading...
Thumbnail Image

Persistent link to this item

Statistics
View Statistics

Journal Title

Journal ISSN

Volume Title

Title

Computational modeling of environmentally relevant reactions

Alternative title

Published Date

2014-07

Publisher

Type

Thesis or Dissertation

Abstract

Computational chemistry is a flexible tool that can quantitatively describe the reactivity of a wide variety of systems, ranging from simple organic molecules to complex heterogenous surfaces. In this thesis, quantum chemical methods are employed in both a diagnostic and predictive capacity to gain insight into the reactions of a number of environmentally relevant chemical systems. Chapter 2 outlines the use of multiple theoretical models for the characterization of the dominant conformers of nerve agents found in aqueous solution and for the understanding of their subsequent inactivation via triethylamine-catalyzed hydrolysis. This computational analysis informed the development of a procedure used to assess the ability of several organic complexes to more efficiently catalyze the decomposition of toxic organophosphates into non-toxic products. Chapter 3 describes the use of Density Functional Theory (DFT) to reveal a complete mechanistic pathway for the oxidation of water by a homogenous copper- bicarbonate catalyst. The proposed mechanistic steps were evaluated by the calculation of redox potentials, pKa values and free energy barriers, which were validated by comparison to experiment. Chapter 4 presents the use of plane-wave periodic DFT to evaluate the details of nitrogen-rich aromatic groups binding to both an aluminum metal surface and two environmentally relevant alumina surfaces. The role that nitrogen substitution on the aromatic ring plays in adsorption on these surfaces was assessed through the analysis of both optimal geometries and computed binding energies.

Keywords

Description

University of Minnesota Ph.D. dissertation. July 2014. Major: Chemistry. Advisor: Professor Christopher J. Cramer. 1 computer file (PDF); xvi, 128 pages.

Related to

Replaces

License

Collections

Series/Report Number

Funding information

Isbn identifier

Doi identifier

Previously Published Citation

Other identifiers

Suggested citation

Winikoff, Stuart. (2014). Computational modeling of environmentally relevant reactions. Retrieved from the University Digital Conservancy, https://hdl.handle.net/11299/165844.

Content distributed via the University Digital Conservancy may be subject to additional license and use restrictions applied by the depositor. By using these files, users agree to the Terms of Use. Materials in the UDC may contain content that is disturbing and/or harmful. For more information, please see our statement on harmful content in digital repositories.