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Geometry optimizations and vibrational analysis were performed using the 6-311G(d,p) basis set with either one of the methods followed by single-point computations using the 6-311+G(d,p) basis set to obtain the total energies according to refs 8 and 9.
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The CBS-Q method is a composite method in which the total energy is derived via a number of steps, one of which is inclusion of a zero-point energy (ZPE) correction, For structures that are not minima on the potential energy surface, no meaningful ZPE correction is obtained, which leads to meaningless total energies.
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95
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0011579067
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note
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2Y substituents. These variations, however, are small (0.01 Å for the alkyl and 0.005 Å for the vinyl systems for either B3LYP or MP2) and do not show any correlation with the reaction enthalpies.
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0011578133
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note
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CBS-Q computations are not performed because inclusion of an extra C1 atom will increase the computational costs drastically. Therefore, we chose to study these leaving-group effects using only the B3LYP and MP2 methods.
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