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Title: Computer modelling for the prediction and analysis of spectroscopic data : application to lyotropic aggregates and transition metal centres
Author: Prior, Christopher
ISNI:       0000 0004 7231 8616
Awarding Body: University of East Anglia
Current Institution: University of East Anglia
Date of Award: 2017
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In this thesis Density Functional Theory (DFT) and Molecular Dynamics (MD) simulations are used to predict, interpret and analyse a range of Electron Paramagnetic Resonance (EPR) and Nuclear Inelastic Scattering (NIS) spectra of di�erent molecular systems. By relating theory and experiment, the models are rigorously tested as well as enabling a clearer interpretation of complex spectra. Firstly, slow motion EPR spectra of microaggregate, micellar, hexagonal and lamellar lyotropic liquid crystal aggregations are investigated for two di�erent surfactant/water systems. Geometric parameters predicted from MD simulations, such as aggregate radii and eccentricity, are compared with experimental data and the dynamics investigated through the use of the Model-Free (MF) approach, allowing for prediction of EPR spectra using the Stochastic Liouville Equation (SLE) in order to relate dynamics and geometry. For the complex hexagonal and lamellar lineshapes, the MF-SLE predicted spectra are compared with those predicted directly and completely from MD. These techniques and simulation approaches are then expanded to the investigation of the structure and dynamics of spin labelled DNA. A scheme for rotation about triple bonds in MD is found to produce good agreement with the spectra observed for acetylene tethered spin labelled DNA using the new parmbsc1 force�eld. The geometry and magnetic parameters of two molybdenum complexes are calculated using DFT. The fast motion EPR spectra are then simulated using these parameters, thereby con�rming the proposed rearrangement of core geometry in the catalytic cycle. Finally, the NIS spectra of a range of iron-sulphur clusters are predicted using DFT for a series of model compounds and hypothetical structures and compared with available experimental spectra. This tests both the accuracy of DFT and the ability of NIS to discriminate between iron sulphur clusters, whilst additionally con�rming spectral assignments.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available