Marcus theory explains photoinduced electron transfer from donor molecules to a fullerene host when all microstates are included, and formation of free charge competes with charge-transfer states.

Understanding how Frenkel excitons efficiently split to form free-charges in low-dielectric constant organic semiconductors has proven challenging, with many different models proposed in recent years to explain this phenomenon. Here, we present evidence that a simple model invoking a modest amount of charge delocalization, a sum over the available microstates, and the Marcus rate constant for electron transfer can explain many seemingly contradictory phenomena reported in the literature. We use an electron-accepting fullerene host matrix dilutely sensitized with a series of electron donor molecules to test this hypothesis. The providing a mechanistic explanation for why Marcus-inverted-behavior is rarely observed in device studies.

The ALEPH Silicon Vertex Detector features an optical fibre laser system to monitor its mechanical stability. The operating principle and the general performance of the laser system are described. The experience obtained during 1997 and 1998 operations confirms the important role that such a system can have with respect to the detector alignment requirements. In particular, the laser system has been used to monitor short-term temperaturerelated effects and long-term movements. These results and a description of the laser-based alignment correction applied to the 1998 data are presented. * Now at Schweizerischer Bankverein, Basel, Switzerland. † Deceased.

Understanding how Frenkel excitons efficiently split to form free-charges in low-dielectric constant organic semiconductors has proven challenging, with many different models proposed in recent years to explain this phenomenon. Here, we present evidence that a simple model invoking a modest amount of charge delocalization, a sum over the available microstates, and the Marcus rate constant for electron transfer can explain many seemingly contradictory phenomena reported in the literature. We use an electron-accepting fullerene host matrix dilutely sensitized with a series of electron donor molecules to test this hypothesis. The donor series enables us to tune the driving force for photoinduced electron transfer over a range of 0.7 eV, mapping out normal, optimal, and inverted regimes for free-charge generation efficiency, as measured by time-resolved microwave conductivity. However, the photoluminescence of the donor is rapidly quenched as the driving force increases, with no evidence for inverted behavior, nor the linear relationship between photoluminescence quenching and charge-generation efficiency one would expect in the absence of additional competing loss pathways. This behavior is self-consistently explained by competitive formation of bound charge-transfer states and long-range or delocalized free-charge states, where both rate constants are described by the Marcus rate equation. Moreover, the model predicts a suppression of the inverted regime for high-concentration blends and efficient ultrafast free-charge generation, providing a mechanistic explanation for why Marcus-inverted-behavior is rarely observed in device studies.