Free inverted regimes

Figure 14 Ti (p, T) vs. temperature for the solvent ethane at fixed density (the critical density) and the theoretically calculated curve. The scaling factor, frequency co, and the hard sphere diameters are the same as those used in the fit of the 34°C density-dependent data, i.e., there are no free parameters in this calculation. Notice the presence of an inverted regime, i.e., a range of temperatures for which the lifetime increases with temperature, contrary to expected behavior. The lifetime peaks at 375 K before decreasing with temperature. Remarkably, the theory captures this phenomenon, though it overestimates the drop in the lifetime with temperature after 375 K.

Figure 9. Free energy dependenee of electron transfer rate (eontinuous line classical treatment, Eq. 14 dotted line quantum treatment, Eq. 10). The three kinetic regimes, normal , activationless , inverted , are shown schematically in terms of classical Marcus parabolae.

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