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Excited states and electron transfer in solution : models based on density functional theory

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dc.contributor.advisor Troy Van Voorhis. en_US Kowalczyk, Timothy Daniel en_US
dc.contributor.other Massachusetts Institute of Technology. Dept. of Chemistry. en_US 2012-09-27T18:11:28Z 2012-09-27T18:11:28Z 2012 en_US 2012 en_US
dc.description Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2012. en_US
dc.description Cataloged from student-submitted PDF version of thesis. en_US
dc.description Includes bibliographical references (p. 161-185). en_US
dc.description.abstract Our understanding of organic materials for solar energy conversion stands to benefit greatly from accurate, computationally tractable electronic structure methods for excited states. Here we apply two approaches based on density functional theory (DFT) to predict excitation energies and electron transfer parameters in organic chromophores and semiconductors in solution. First, we apply constrained DFT to characterize charge recombination in a photoexcited donor-acceptor dyad and to understand the photophysical behavior of a fluorescent sensor for aqueous zinc. Second, we discover that the delta-self-consistent-field ([Delta]SCF) approach to excited states in DFT offers accuracy comparable to that of the better-established but more indirect linear-response time-dependent DFT approach, and we offer some justification for the similarity. Finally, we investigate a spin-restricted analog of [Delta]SCF known as restricted open-shell Kohn-Sham (ROKS) theory. We resolve a known ambiguity in the formal solution of the ROKS equations for the singlet excited state by presenting a self-consistent implementation of ROKS with respect to the mixing angle between the two open shells. The excited state methods developed and applied in this work contribute to the expanding toolkit of electronic structure theory for challenging problems in the characterization and design of organic materials. en_US
dc.description.statementofresponsibility by Timothy Daniel Kowalczyk. en_US
dc.format.extent 185 p. en_US
dc.language.iso eng en_US
dc.publisher Massachusetts Institute of Technology en_US
dc.rights 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. en_US
dc.rights.uri en_US
dc.subject Chemistry. en_US
dc.title Excited states and electron transfer in solution : models based on density functional theory en_US
dc.type Thesis en_US Ph.D. en_US
dc.contributor.department Massachusetts Institute of Technology. Dept. of Chemistry. en_US
dc.identifier.oclc 809562721 en_US

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