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Additional resources for Photoelectrochemical Solar Conversion Systems: Molecular and Electronic Aspects

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Some compounds showing this phenomenon (bottom). 21 shows an energy band diagram and the main electronic processes for an illuminated idealized pn-junction. Under electronic equilibrium both phases adopt the same Fermi-level, requiring a band bending at the limit with the electrolyte. The alignment of the Fermi levels at the contact will be achieved by a tunnel p+-n+-junction. This type of contact ensures on the one hand a rapid annihilation of the majority charge carriers generated by separation of photo-induced electron-hole pairs.

The former case can be interpreted as an electronic delocalization with frozen molecular coordinates at the transfer point. This case is generally described by a classical treatment of the molecular oscillation of the solvation shell of the electroactive particles. The nonadiabatic transfer requires a more complex analysis and is particularly suited for the description of long-range electron transfer processes. 62) with zA and zD as the coordinates of the acceptor and donor, respectively. In the case of a coupling of the electron transfer with high frequency states of the inner molecular structure and low frequency states of the surrounding solvent, the whole process can be described by a quantum mechanical–classical treatment, where the high frequency modes are quantum mechanical and the low frequency modes are classically described.

Single exciton splitting was also observed in several polymers such as polydiacetylene [109], poly(p-phenylene vinylene), and poly(p-phenylene) [110] as well as in charotenoides [111] and covalent tetracene [112] and 1,3-diphenylisobenzofuran dimmers [114]. 20. Here, it is assumed that the molecules behave as harmonic oscillators, and thus the potential energy is represented as a parabola. Electrons are excited from their ground states S0 to a permitted energy vibration level (S1*) of the excited state (S1) by illumination.

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