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A reviewer points out that it is conceivable that bromine or other heavy atoms could result in a heavy atom effect in coumarin but not in a transition metal radical cage pair. Specifically, this situation could result if the rate enhancement caused by the heavy atom is comparable to (or faster than) the ISC rate in coumarin but slower than the ISC rate in the transition metal radical cage pair. As shown in the next section, the transition metal cage pairs recombine on the timescale of 5 ps. The timescale of ISC in the transition metal cage pair would thus have to be shorter than 5 ps for this situation to apply. In any case, a radical-radical recombination reaction with a 5 ps timescale would not traditionally be considered to have a spin barrier
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A reviewer points out that it is conceivable that bromine or other heavy atoms could result in a heavy atom effect in coumarin but not in a transition metal radical cage pair. Specifically, this situation could result if the rate enhancement caused by the heavy atom is comparable to (or faster than) the ISC rate in coumarin but slower than the ISC rate in the transition metal radical cage pair. As shown in the next section, the transition metal cage pairs recombine on the timescale of 5 ps. The timescale of ISC in the transition metal cage pair would thus have to be shorter than 5 ps for this situation to apply. In any case, a radical-radical recombination reaction with a 5 ps timescale would not traditionally be considered to have a spin barrier.
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94
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34249072962
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The choice of a suitable heavy-atom-containing molecule for use in pump-probe experiments required that the compound be inert toward reaction with the transient radical species, that it not absorb at wavelengths used in the study, and that it has minimal second- and third-order non-linear optical susceptibility coefficients, χ(2) and χ3, to eliminate artifacts that would obscure the results
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(3), to eliminate artifacts that would obscure the results.
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95
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0041887254
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Schutte, E.; Weakley, T. J. R.; Tyler, D. R. J. Am. Chem. Soc. 2003, 125, 10319-10326.
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Schutte, E.1
Weakley, T.J.R.2
Tyler, D.R.3
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Braden, D. A.; Parrack, E. E.; Tyler, D. R. Photochem. Photobiol. Sci. 2002, 1, 418-420.
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(2002)
Photochem. Photobiol. Sci
, vol.1
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Braden, D.A.1
Parrack, E.E.2
Tyler, D.R.3
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