This investigation explored whether there is a spin barrier to recombination of first- and second-row transition metal-centered radicals in a radical cage pair. To answer this question, the recombination efficiencies of photochemically generated radical cage pairs (denoted as FcP) were measured in the presence and absence of an external heavy atom probe. Two methods were employed for measuring the cage effect. The first method was femtosecond pump-probe transient absorption spectroscopy, which directly measured FcP from reaction kinetics, and the second method (referred to herein as the "steady-state" method) obtained FcP from quantum yields for the radical trapping reaction with CCl4 as a function of solvent viscosity. Both methods generated radical cage pairs by photolysis (lambda = 515 nm for the pump probe method and lambda = 546 nm for the steady-state method) of Cp'2Mo2(CO)6 (Cp' = eta(5)-C5H4CH3). In addition, radical cage pairs generated from Cp'2Fe2(CO)4 and Cp*2TiCl2 (Cp* = eta(5)-C5(CH3)5) were studied by the steady-state method. The pump-probe method used p-dichlorobenzene as the heavy atom perturber, whereas the steady-state method used iodobenzene. For both methods and for all the radical caged pairs investigated, there were no observable heavy atom effects, from which it is concluded there is no spin barrier to recombination.

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This article outlines the difficulties associated with measuring quantum yields for solid-state samples using a high-pressure mercury arc lamp as the irradiation source. Details are given for the conversion of an inexpensive frequency-doubled neodymium-doped yttrium aluminum garnet (Nd:YAG) diode laser pointer module into a viable irradiation source. The modified Nd:YAG laser was incorporated into a computer-controlled system, which allowed for the simultaneous irradiation and spectroscopic monitoring of the sample. The data obtained with the Nd:YAG diode laser system show far less scatter than data obtained with a high-pressure Hg arc lamp, and consequently the degradation rates obtained with the laser system could be calculated with far greater accuracy.

We have investigated the possibility that variations in the level of intracellular Ca2+ in excitable cells might be induced as an artifact of the incoherent illumination that is being used to monitor transient responses. In order to avoid the fluctuations in power of an arc lamp source, a microscope using a light emitting diode that was calibrated accurately at low power levels, was constructed to provide good control over the dose of light applied to the biological specimen. We report here that higher powers of illumination increased the probability of occurrence of Ca2+ transients even in the sub-mW range normally used to measure such transients in epi-fluorescence work, suggesting that caution should be exercised when designing experiments and interpreting data.