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By asymmetrically substituted compound, when applied to diazenes or ketones, we mean here a diazene or carbonyl group bound to two different groups on either side, yielding two different free alkyl radicals by photolysis
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By asymmetrically substituted compound, when applied to diazenes or ketones, we mean here a diazene or carbonyl group bound to two different groups on either side, yielding two different free alkyl radicals by photolysis.
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Photolysis of an asymmetrically substituted diazene in supercritical fluids and compressed gases: A cage effect study
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Hoijemberg, P. A.; Zerbs, J.; Japas, M. L.; Chesta, C. A.; Schroeder, J.; Aramendía, P. F. Photolysis of an asymmetrically substituted diazene in supercritical fluids and compressed gases: a cage effect study. J. Phys. Chem. A, in press.
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published online March 30
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66149126731
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esc) [t-Bu]/[BME] (4) If we make the assumption that rate constants for the radical reactions and cage factors for the different radical encounters are all equal, then the concentrations of the two radicals are equal, and we arrive at the expression given in the text.
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esc) [t-Bu]/[BME] (4) If we make the assumption that rate constants for the radical reactions and cage factors for the different radical encounters are all equal, then the concentrations of the two radicals are equal, and we arrive at the expression given in the text.
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We assume that there is no difference in the photochemistry of the diazene between 254 nm excitation (steady-state experiments where f- diazenewas determined) and 266 nm excitation nanosecond pulses used to obtain the data in Figure 4
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diazenewas determined) and 266 nm excitation (nanosecond pulses used to obtain the data in Figure 4).
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Turro, N. J. Chapter 9. In Modern Molecular Photochemistry; University Science Books: Mill Valley, CA, 1991; p 314.
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