The studies presented in this thesis explore energy transfer and relaxation in excitonic systems using two types of third-order non-linear spectroscopy, transient grating (TG) and two-dimensional photon echo (2DPE). Two major excitonic systems are studied, colloidal CdSe nanocrystals and a photosynthetic system, the light harvesting antenna protein PE545 isolated from cryptophyte algae Rhodomonas CS24.
The inhomogeneous broadening present in colloidal samples has long been an obstacle to the study of the fine structure of CdSe nanocrystals. This thesis will present two studies, each using a different spectroscopy to overcome this problem and gain insight into the fine structure of the ground state exciton and biexciton. In both cases, polarization dependent measurements are used to isolate particular types of pathways through the fine structure.
Polarization dependent TG measurements and a detailed kinetic model have allowed us to identify major pathways for excitonic relaxation within the fine structure of the ground state exciton, despite the inhomogeneous broadening present in the sample. Conclusions from this work include an analogy to the internal conversion and intersystem crossing transitions in molecules, concepts which are familiar to most chemists.
Polarization dependent 2DPE experiments and a simulation of the resulting spectra have allowed for the direct observation of the ground state biexcitonic fine structure. The high density of states in the spectral region of the biexciton obscures these states in most spectroscopies, but the combination of polarization dependence and the use of a two-dimensional technique have revealed these elusive fine structure states.
This 2DPE technique is then used to inspect light harvesting antenna protein PE545, a system of eight chromophores covalently bonded to a protein scaffold. The 2DPE measurement is capable of identifying oscillatory components of the signal which are signatures of coherent energy sharing. Using this technique, coherent energy sharing is observed throughout the spectrum of the protein at ambient temperatures, and control experiments suggest that the observed coherences are electronic, not vibrational.
A short study is also presented which compares the utility of two approximations for calculations of electronic coupling and energy transfer in elongated excitonic systems.
| Identifer | oai:union.ndltd.org:TORONTO/oai:tspace.library.utoronto.ca:1807/29911 |
| Date | 31 August 2011 |
| Creators | Wong, Cathy Yat-Yee |
| Contributors | Scholes, Gregory D. |
| Source Sets | University of Toronto |
| Language | en_ca |
| Detected Language | English |
| Type | Thesis |
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