Hydrogen-Atom Abstraction from Alkanes by OH. 4 ... - ACS Publications

EM, the argument of the Bessel function in R, is nS,(ii(ii + 1))'12. >> 1 and the asymptotic expansion for this function can be applied. The condition...
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J. Phys. Chem. 1986,90, 5932-5937

5932

After some algebra, the condition (10) takes on the form -(2H

AE + 1)so + --(In hw

[(A

+ l ) E ~ / h E l+ 1) 0.5 In (AE hw)

If hw/kBT >> 1, then ii to

-So

+ E[ln hw

i=

(EM/AE)

>> -10.594

(11)

0, and this condition can be simplified

+ 11 - 0.5 In (AEhw) > -10.594 (12)

(b) For the case of high temperatures ( h o / k B T> 1 and the asymptotic expansion for this function can be applied. The condition (10) takes on the form

+

On the basis of the relations (1 l ) , (12), or (1 3), it is possible to determine the range of parameters favoring, say, the nonradiative capture. For instance, if the matrix is characterized by the parameters Soand h w , the nonradiative capture is preferred by the traps with the depth lEtl obeying the conditions lE,l[ln (EM) + 11 - lil (lEtl)(lEtl - 0.5hw) > hw(0.5 In (hw) - 10.594) + E M (14) at low temperatures ( h w / k B T >> 1) and E M - 3 k ~ T / 2- X € lEtl E M - 3 k ~ T / 2+ X

(15)

x = ~ ( E M ~ B10.247 T [ - 0.5 In (Ehlk~r)])”’ at high temperatures ( h w / k B T