Multidimensional tunneling calculations are carried out for 13 reactions, to test the scope of heavy-atom tunneling in organic chemistry, and to check the accuracy of one-dimensional tunneling models. The reactions include pericyclic, cycloaromatization, radical cyclization and ring opening, and S 2. When compared at the temperatures that give the same effective rate constant of 3×10 s , tunneling accounts for 25-95 % of the rate in 8 of the 13 reactions. Values of transmission coefficients predicted by Bell's formula, κ , agree well with multidimensional tunneling (canonical variational transition state theory with small curvature tunneling), κ . Mean unsigned deviations of κ vs. κ are 0.08, 0.04, 0.02 at 250, 300 and 400 K. This suggests that κ is a useful first choice for predicting transmission coefficients in heavy-atom tunnelling.
Multidimensional tunneling calculations are carried out for 13 reactions,tot est the scope of heavy-atom tunneling in organic chemistry,a nd to check the accuracy of onedimensional tunneling models.T he reactions include pericyclic, cycloaromatization, radical cyclization and ring opening, and S N 2. When compared at the temperatures that give the same effective rate constant of 3 10 À5 s À1 ,t unneling accounts for 25-95 %o ft he rate in 8o ft he 13 reactions.V alues of transmission coefficients predicted by Bellsf ormula, k Bell , agree well with multidimensional tunneling (canonical variational transition state theory with small curvature tunneling), k SCT .M ean unsigned deviations of k Bell vs. k SCT are 0.08, 0.04, 0.02 at 250, 300 and 400 K. This suggests that k Bell is au seful first choice for predicting transmission coefficients in heavyatom tunnelling.
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