-
7
-
-
84906411385
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-
+, respectively, indicate hydrogenation and protonation.
-
+, respectively, indicate hydrogenation and protonation.
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8
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84906382606
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To obtain fully completed geometry optimizations in some cases, it was necessary to use the "OPT=CALCALL" option; accordingly, all geometries and frequencies for the individual-molecule cases were obtained with this approach.
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We note that all absolute energies decreased with increasing ε, as expected. The increased relative energies shown in Table 1 for some molecules reflect the magnitude of their dipole moments in comparison to that of the parent. When placed within a dielectric, the energy of a neutral molecule will decrease in proportion to the square of its dipole moment Onsager's model of the dipole reaction field, Thus, with increasing ε, the parent's energy will decrease more rapidly than that of another neutral form with a smaller dipole moment: see: Onsager, L. J. Am. Chem. Soc. 1936, 58, 1486
-
We note that all absolute energies decreased with increasing ε, as expected. The increased relative energies shown in Table 1 for some molecules reflect the magnitude of their dipole moments in comparison to that of the parent. When placed within a dielectric, the energy of a neutral molecule will decrease in proportion to the square of its dipole moment (Onsager's model of the dipole reaction field). Thus, with increasing ε, the parent's energy will decrease more rapidly than that of another neutral form with a smaller dipole moment: see: Onsager, L. J. Am. Chem. Soc. 1936, 58, 1486.
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We found a candidate for the transition structure connecting the pre- and post-transferred geometries of the reduction product in water that suggested forward and reverse barriers of 10.0 and 30.6 kJ/mol, respectively. These indicate a forward barrier that is quite low, 2.4 kcal/mol, Unfortunately, we were unable to confirm this as the correct transition structure because the IRC calculation did not go to completion
-
We found a candidate for the transition structure connecting the pre- and post-transferred geometries of the reduction product in water that suggested forward and reverse barriers of 10.0 and 30.6 kJ/mol, respectively. These indicate a forward barrier that is quite low (-2.4 kcal/mol). Unfortunately, we were unable to confirm this as the correct transition structure because the IRC calculation did not go to completion.
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