Text

theses

The research described in this dissertation consists of two projects. First, the application and improvement of a subsystem DFT method to describe charge transfer reactions in biosystems and molecular materials. Second, the development and validation of a constrained subsystem DFT method to model charge and excitation energy transfer processes in molecules and condensed phases. After introducing the theory of charge transfer reactions in condensed phases (chapter 1), the candidate outlines original and well-established avenues to obtain the electronic couplings (the key parameter to understand the dynamics of these processes). The first project is presented in chapter 3, in which a benchmark study against high-level methods is presented followed by the analysis of the environmental effects on the hole transfer in DNA oligomers. In chapter 4 the advantages of the candidate's method are pointed out, especially its ability to combine Constrained DFT and subsystem DFT formalisms. Such a flexible method enables the study of the effects of the phosphate group on hole transfer couplings in DNA for the first time in the literature. Additional applications of this method are given in chapter 5, where the quality of the calculated excited states is examined. Finally, in the last chapter two applications are presented: modeling of (1) the hole transfer in Fe-TPP dyads; and (2) charge transfer in the peptidylglycine-α-hydroxylating monooxygenase enzyme. Every project is published or in the process to be published by the candidate in co-authorship with the candidate's scientific advisor and other collaborators in peer-reviewed journals.

ETD_8718

Ph.D.

Includes bibliographical references

by Pablo Ramos

doi:10.7282/T30K2D14

ETD doctoral

The author owns the copyright to this work.