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Quantum Coherence for Light Harvesting
Paleček, David ; Dědic, Roman (advisor) ; Jonas, David M. (referee) ; Polívka, Tomáš (referee)
Almost all life on Earth depends on the products of photosynthesis - the biochemical process whereby solar energy is stored as chemical-rich compounds. The energy of captured photons is transferred through a network of pigment-protein complexes towards the reaction center. The reaction center is responsible for trans-membrane charge separation, which generates a proton motive force which drives all subsequent biochemical reactions. The ultrafast (femtosecond) nature of the primary processes in photosynthesis is the main reason for its astonishing efficiency. On this timescale, quantum effects start to play a role and can appear in measured spectra as oscillations. It has been hypothesized that these are evidence of wave-like energy transfer. To unveil the fundamental principals of ultrafast excitation energy transfer in both natural and artificial light-harvesting systems, advanced spectroscopy techniques have been utilized. Coherent two- dimensional electronic spectroscopy is a state of the art technique which allows the most complete spectroscopic and temporal information to be extracted from the system under study. This technique has allowed us to identify a new photophysical process where the coherence of the initially excited state is shifted to the ground state upon an energy transfer step. Coherence...
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Role of system-bath interaction time-scales in photosynthetic excitation energy transfer
Malý, Pavel ; Mančal, Tomáš (advisor) ; Croce, Roberta (referee) ; Polívka, Tomáš (referee)
ROLE ASOVÉ 'KÁLY INTERAKCE SYSTÉM-LÁZE VE FOTOSYNTETICKÉM P ENOSU EXCITANÍ ENERGIE Tato práce se věnuje vlivu rychlého a pomalého molekulárno pohybu na přenos excitační energie ve fotosyntetick- ých světlosběrných komplexech. Vyvinuli jsme nový teoretický popis vnitromolekulárních vibračních mod· a zjistili jsme, že jejich resonance s energetickými rozdíly mezi fotosyntetickými pigmenty m·že vést ke zrychlení přenosu energie. Použitím jednomolekulární spektroskopie jsme pozorovali jak pomalé změny bílkovinné konformace mohou zcela změnit stav světlosběrného komplexu LHCII vyšších rostlin. Také jsme vyvinuli novou experimentální techniku, dvoupulzní ultrarychlou jednomolekulární spektroskopii. S její pomocí m·žeme pozorovat jak pomalý pohyb bílkoviny bakteriální antény LH2 ovlivňuje ultrarychlou relaxaci energie uvnitř komplexu. Konstrukcí jednotného modelu pro ultrarychlé objemové a jednomolekulární experimenty se nám podařilo zakomponovat rychlou a pomalou časovou škálu molekulárního pohybu do jednoho pohledu na fotosyntetický sběr světla.
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Carotenoid Excited State Processes by Femtosecond Time-Resolved Pump-Probe and Multi-Pulse Spectroscopies
WEST, Robert G.
This Ph.D. thesis is an exploration of carotenoids by ultrafast, time-resolved absorption spectroscopy to investigate their complicated relaxation processes, means of energy transfer, and dependence on structure. The introduction begins with an overview of carotenoids, intended for the reader to appreciate their importance and their complexity as revealed by decades of research in carotenoid photophysics. To understand the primary concerns of this research field, the reader is guided through basic theory of energetic processes, the experimental method, and methods of analysis. The main body of the text is the Research Chapter, containing four sections, each describing research using varied ultrafast transient absorption spectroscopies on carotenoids in solution and when bound to a host protein. Section 2.1 concerns an equilibration phenomenon in the lowest excited state of the carotenoid fucoxanthin in various solutions and temperatures by a multi-pulse transient absorption method. The same method is applied to fucoxanthin in a host antennae protein of the pennate diatom Phaeodactylum tricornutum to investigate the function of the equilibration in energy transfer to Chlorophyll a in Section 2.2. The next two sections regard the effect of carotenoid structure on its relaxation dynamics. Section 2.3 investigates the effect of the non-conjugated acyloxy group of two fucoxanthin derivatives in various solvents. Here, one of the energetic states involved in the equilibrium mentioned above is seen drastically affected. Lastly, Section 2.4 investigates alloxanthin, a carotenoid with an unusual pair of carbon-carbon triple bonds. Their effect on the conjugation is evaluated based upon the molecules' decay dynamics. A general summary and conclusion is provided at the end.
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Quantum Coherence for Light Harvesting
Paleček, David ; Dědic, Roman (advisor) ; Jonas, David M. (referee) ; Polívka, Tomáš (referee)
Almost all life on Earth depends on the products of photosynthesis - the biochemical process whereby solar energy is stored as chemical-rich compounds. The energy of captured photons is transferred through a network of pigment-protein complexes towards the reaction center. The reaction center is responsible for trans-membrane charge separation, which generates a proton motive force which drives all subsequent biochemical reactions. The ultrafast (femtosecond) nature of the primary processes in photosynthesis is the main reason for its astonishing efficiency. On this timescale, quantum effects start to play a role and can appear in measured spectra as oscillations. It has been hypothesized that these are evidence of wave-like energy transfer. To unveil the fundamental principals of ultrafast excitation energy transfer in both natural and artificial light-harvesting systems, advanced spectroscopy techniques have been utilized. Coherent two- dimensional electronic spectroscopy is a state of the art technique which allows the most complete spectroscopic and temporal information to be extracted from the system under study. This technique has allowed us to identify a new photophysical process where the coherence of the initially excited state is shifted to the ground state upon an energy transfer step. Coherence...
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