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more..
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47
-
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0345891702
-
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note
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The RHF calculations predict that a very loose π-complex is formed without a barrier on the approach of singlet oxygen to the pi bond of tetramethylethylene. The energy of the π-complex was -1.1 kcal/mol relative to those of the separate alkene and singlet oxygen. After allowance for basis set superposition error and entropy, this "complex" is unlikely to correspond to a free-energy minimum at 25 °C.v
-
-
-
-
48
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0346522498
-
-
note
-
Spin-projected UB3LYP/6-311++G** puts 18 1.2 kcal/mol above the energy of 17 and 19 5.2 kcal/mol above the energy of 17, virtually identical to the spin-projected UB3LYP/6-31G* energetics.
-
-
-
-
49
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0024841752
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For the calculations, the program QUIVER was used (Saunders, M.; Laidig, K. E.; Wolfsberg, M. J. Am. Chem. Soc. 1989, 111, 8989) with Becke3LYP and RHF frequencies scaled by 0.9614 and 0.91, respectively (Scott, A. P.; Radom, L. J. Phys. Chem. 1996, 100, 16502).
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0011083273
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For the calculations, the program QUIVER was used (Saunders, M.; Laidig, K. E.; Wolfsberg, M. J. Am. Chem. Soc. 1989, 111, 8989) with Becke3LYP and RHF frequencies scaled by 0.9614 and 0.91, respectively (Scott, A. P.; Radom, L. J. Phys. Chem. 1996, 100, 16502).
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0347782945
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note
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s-symmetric structures by successively decreasing X by 0.1 Å, leaving Y constant, and reoptimizing the geometry at each step.
-
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-
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58
-
-
0346522497
-
-
note
-
As the structure departs from the saddle point along the MEP, a low-energy rotational mode in the nonreacting methyl group is loosened, and overall, the entropy is increasing (on the basis of B3LYP frequencies, 298 K). There is thus no indication of a free-energy barrier to the decomposition of the perepoxide.
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