Basic Research Needs for Solar Energy Utilization - Office of ...
Basic Research Needs for Solar Energy Utilization - Office of ...
Basic Research Needs for Solar Energy Utilization - Office of ...
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Efficient Photo-initiated Charge Separation and Storage. The dependence <strong>of</strong> the rates <strong>of</strong><br />
electron transfer reactions within covalently linked donor-acceptor molecules on the free energy<br />
<strong>of</strong> the reaction and the electronic interaction between the donor and the acceptor are described<br />
well by theory (Marcus 1956). Both theory and experiment show that there is an optimal free<br />
energy <strong>for</strong> achieving the maximum electron transfer rate, and there<strong>for</strong>e the maximum efficiency,<br />
<strong>for</strong> this process. Moreover, a key prediction <strong>of</strong> theory is that the rate <strong>of</strong> an electron transfer<br />
reaction will slow when the free energy <strong>of</strong> the reaction becomes very large. The key to observing<br />
this so-called “inverted region” in donor-acceptor molecules is maintaining a fixed distance<br />
between the donor and the acceptor as the structure <strong>of</strong> the donor and/or the acceptor is changed<br />
to modify the free energy (Miller et al. 1984; Wasielewski et al. 1985). The use <strong>of</strong> large free<br />
energies <strong>for</strong> charge recombination to slow these energy-wasting reactions is critical to achieving<br />
the long charge separation times essential <strong>for</strong> driving catalysts <strong>for</strong> fuel <strong>for</strong>mation.<br />
Another important prediction <strong>of</strong> electron transfer theory is that the rates (and efficiencies) <strong>of</strong><br />
electron transfer generally decrease exponentially as a function <strong>of</strong> distance. Experiments have<br />
confirmed this exponential distance dependence and have shown that the steepness <strong>of</strong> this<br />
dependence reflects the molecular structure <strong>of</strong> the molecules linking the electron donor to the<br />
acceptor. Rates <strong>of</strong> electron transfer reactions generally decrease by about a factor <strong>of</strong> 30 <strong>for</strong> every<br />
1 nm <strong>of</strong> distance (Paddon-Row et al. 1988).<br />
The various electron donors and acceptors used in bio-inspired artificial photosynthetic systems<br />
need not be covalently linked to one another. In fact, natural photosynthetic systems use the<br />
surrounding protein to position the chlorophyll electron donors and suitable acceptors close to<br />
one another. The nature <strong>of</strong> non-covalent interactions among electron donors and acceptors, such<br />
as those found in molecules ranging from DNA to the bacterial photosynthetic RC, is an<br />
important area <strong>of</strong> investigation. Non-covalent assemblies may be constructed through a variety<br />
<strong>of</strong> weak chemical interactions between molecules, e.g., hydrogen bonding, coordination bonding,<br />
π-π stacking, <strong>for</strong>mation <strong>of</strong> donor-acceptor charge transfer complexes, and electrostatic<br />
interactions. For example, it has been shown that photogenerated positive charges can move<br />
within DNA by means <strong>of</strong> non-covalent interactions between the stacked base pairs (Lewis et al.<br />
1997).<br />
The importance <strong>of</strong> using a cascade <strong>of</strong> thermal electron transfer steps following the initial<br />
photoinduced charge separation, as evidenced by natural photosynthesis, has been demonstrated<br />
in numerous systems. Studies on the optimization <strong>of</strong> the free energy changes, distances, and<br />
orientations between the various donors and acceptors have allowed researchers to determine<br />
strategies <strong>for</strong> the development <strong>of</strong> novel molecular structures to tailor the charge separation and<br />
storage characteristics to specific applications. For example, efficient per<strong>for</strong>mance in the solid<br />
state requires (1) the use <strong>of</strong> specialized donor and/or acceptor molecules, such as C60, that<br />
undergo minimal structural changes following electron transfer, or (2) the incorporation <strong>of</strong> highpotential<br />
donors and acceptors to overcome the inability <strong>of</strong> the solvent to change its structure in<br />
the solid state. In these systems, photoinduced charge separation, followed by 1–3 thermal<br />
electron transfer steps, leads to overall charge separation efficiencies <strong>of</strong> about 80% that persist<br />
<strong>for</strong> times approaching seconds (Gust et al. 2001; Wasielewski 1992). Ultrafast laser techniques<br />
that measure events down to 20 fs (20 quadrillionths <strong>of</strong> a second), as well as time-resolved<br />
measurements <strong>of</strong> the magnetic properties <strong>of</strong> charged intermediates produced within these<br />
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