DOE OSTI2019
The efficient conversion of sunlight to a useful form of energy both in green plants and in manmade dye-sensitized solar cells requires the efficient separation of a positive and negative charge. The charge separation process begins with the absorption of visible or ultraviolet light by a pigment such as chlorophyll or a dye such as a transition metal complex followed by fast electron transfer to a neighboring molecule to form a pair of ionized molecules with opposite charges. At that point, one of the two opposite charges must rapidly move away from the other one by the process of charge separation. Once the migrating charge reaches its destination, it can be converted to electrical or chemical energy. The overall efficiency of charge separation in these systems is determined by the competition between charge separation and charge recombination at each stage in the process. Whereas most investigations of photoinduced charge separation have employed synthetic polymers or covalent linkages to separate the photoactive molecular and charge acceptor, we have employed the natural biopolymer DNA for this purpose. DNA possesses a unique structure consisting of a hydrophobic core of hydrogen-bonded base pairs which form a one-dimensional π-stacked array. The possibility that the π-stacked base pairs of DNA might function as a one-dimensional conductor or molecular wire was first advanced over 50 years ago. However, systematic measurements of the dynamics and efficiency of charge separation in DNA-based systems were not undertaken prior to the initiation of our studies 22 years ago. A variety of organic chromophores can be attached to one or both ends of the base pair domain of DNA or at any location within the domain. The length and base sequence of the base pair domain can also be varied. The structures of these synthetic derivatives of DNA have been determined using a combination of X-ray diffraction, NMR spectroscopy, and molecular modeling. Selective excitation with UV or visible light of the appropriate chromophore can effect injection of either positive charge (holes) or negative charge (electrons) into the base pair domain. The dynamics of hole or electron injection can be studied by a combination of fluorescence quenching and transient absorption measurements. Moreover, the simple design of our systems is amenable to theoretical modeling, allowing the development and testing of models which may prove applicable to more complex systems. Our initial studies of hole transport in short synthetic DNA with either repeating or alternating base sequences showed it to be strongly distance dependent, seemingly contradicting claims that DNA might serve as a wire in molecular electron devices. Further research on the base-sequence dependence of hole transport dynamics showed that significant enhancement in hole transport dynamics could be achieved by the used of special sequences designed to prevent the photo-generated charges from recombining. More recent experimental research and theoretical modelling has served to define each stage of the charge-separation process: electronic excitation, hole injection, hole transport, hole transport, and charge recombination. DNA is less effective as a carrier for electron transport; however, many of these details have also been determined for this process. In summary, a combination of molecular design and synthesis, spectroscopy, and theory have made possible the most complete study of photoinduced charge separation on any complex donor-bridge-acceptor system studied to date. These results serve as a benchmark to which related studies can be compared.