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Troy Van Voorhis. Mavros, Michael G. (Michael George) Massachusetts Institute of Technology. Department of Chemistry. Massachusetts Institute of Technology. Department of Chemistry 2016-10-25T19:16:37Z 2016-10-25T19:16:37Z 2016 2016 http://hdl.handle.net/1721.1/104975 959710309 Thesis: Ph. D., Massachusetts Institute of Technology, Department of Chemistry, 2016. This electronic version was submitted by the student author. The certified thesis is available in the Institute Archives and Special Collections. Cataloged from student-submitted PDF version of thesis. Includes bibliographical references (pages 121-145). A mechanistic understanding of electron transfer in solution will advance our understanding of many chemical processes, including heterogeneous redox catalysis and photochemistry-processes which are fundamental in energy storage and solar energy conversion, among other applications. In this thesis, we first apply density functional theory (DFT) to study the mechanistic intermediates of the oxygen evolution reaction (OER) on metal-oxide redox catalysts. From these thermodynamic calculations, we are able to gain insight into catalytic design principles. Afterwards, we study nonadiabatic electron transfer in solution. After benchmarking various resummations of a fourth-order perturbation theory expansion of a generalized master equation memory kernel for the spin-boson model, we apply our theoretical understanding to study the short-time dynamics of electron transfer beyond the Condon approximation in aqueous iron(II) / iron(III) electron self-exchange. We discuss the application of this method to identify conical intersections in condensed-phase photochemistry. Finally, we examine the range of validity of electron couplings predicted by constrained density functional theory with configuration interaction (CDFT-CI). The nonadiabatic electron transfer methods developed and applied in this work will contribute to a relatively sparse computational toolkit for studying challenging problems in photochemical electron transfer, such as the prediction of nonradiative decay rates from first principle; these, in turn, will contribute to the design of catalytic materials for solar energy conversion. by Michael G. Mavros. Ph.D. 142 pages eng Massachusetts Institute of Technology M.I.T. theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. See provided URL for inquiries about permission. http://dspace.mit.edu/handle/1721.1/7582 Chemistry. Electron transfer in solution : nonadiabatic dynamics and applications to catalysis Thesis application/pdf Publication unknown unknown <Publication xmlns="https://www.openaire.eu/cerif-profile/1.1/" id="566efc06-dcc3-4862-b0b0-bde01d3753ce"> <Type xmlns="https://www.openaire.eu/cerif-profile/vocab/COAR_Publication_Types">http://purl.org/coar/resource_type/c_1843</Type> <Language>eng</Language> <Title>Electron transfer in solution : nonadiabatic dynamics and applications to catalysis</Title> <PublishedIn> <Publication> </Publication> </PublishedIn> <PublicationDate>2016</PublicationDate> <Authors> <Author> <DisplayName>Mavros, Michael G. (Michael George)</DisplayName> <Affiliation> <OrgUnit> </OrgUnit> </Affiliation> </Author> </Authors> <Editors> </Editors> <Publishers> <Publisher> <DisplayName>Massachusetts Institute of Technology</DisplayName> <OrgUnit /> </Publisher> </Publishers> <License>http://dspace.mit.edu/handle/1721.1/7582</License> <Keyword>Chemistry.</Keyword> <Abstract>A mechanistic understanding of electron transfer in solution will advance our understanding of many chemical processes, including heterogeneous redox catalysis and photochemistry-processes which are fundamental in energy storage and solar energy conversion, among other applications. In this thesis, we first apply density functional theory (DFT) to study the mechanistic intermediates of the oxygen evolution reaction (OER) on metal-oxide redox catalysts. From these thermodynamic calculations, we are able to gain insight into catalytic design principles. Afterwards, we study nonadiabatic electron transfer in solution. After benchmarking various resummations of a fourth-order perturbation theory expansion of a generalized master equation memory kernel for the spin-boson model, we apply our theoretical understanding to study the short-time dynamics of electron transfer beyond the Condon approximation in aqueous iron(II) / iron(III) electron self-exchange. We discuss the application of this method to identify conical intersections in condensed-phase photochemistry. Finally, we examine the range of validity of electron couplings predicted by constrained density functional theory with configuration interaction (CDFT-CI). The nonadiabatic electron transfer methods developed and applied in this work will contribute to a relatively sparse computational toolkit for studying challenging problems in photochemical electron transfer, such as the prediction of nonradiative decay rates from first principle; these, in turn, will contribute to the design of catalytic materials for solar energy conversion.</Abstract> <Access xmlns="http://purl.org/coar/access_right" > </Access> </Publication>