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dc.contributor.advisorTroy Van Voorhis.en_US
dc.contributor.authorMavros, Michael G. (Michael George)en_US
dc.contributor.otherMassachusetts Institute of Technology. Department of Chemistry.en_US
dc.date.accessioned2016-10-25T19:16:37Z
dc.date.available2016-10-25T19:16:37Z
dc.date.copyright2016en_US
dc.date.issued2016en_US
dc.identifier.urihttp://hdl.handle.net/1721.1/104975
dc.descriptionThesis: Ph. D., Massachusetts Institute of Technology, Department of Chemistry, 2016.en_US
dc.descriptionThis electronic version was submitted by the student author. The certified thesis is available in the Institute Archives and Special Collections.en_US
dc.descriptionCataloged from student-submitted PDF version of thesis.en_US
dc.descriptionIncludes bibliographical references (pages 121-145).en_US
dc.description.abstractA 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.en_US
dc.description.statementofresponsibilityby Michael G. Mavros.en_US
dc.format.extent142 pagesen_US
dc.language.isoengen_US
dc.publisherMassachusetts Institute of Technologyen_US
dc.rightsM.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.en_US
dc.rights.urihttp://dspace.mit.edu/handle/1721.1/7582en_US
dc.subjectChemistry.en_US
dc.titleElectron transfer in solution : nonadiabatic dynamics and applications to catalysisen_US
dc.typeThesisen_US
dc.description.degreePh. D.en_US
dc.contributor.departmentMassachusetts Institute of Technology. Department of Chemistry
dc.identifier.oclc959710309en_US


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