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note
-
Maximum and average differences between the results of the MP2/6-311+G(3df,2p) and MP2/6-311++G(d,p) calculations for compounds 1-12 are 0.029 Å (for 11t) and 0.007 Å in bond length, respectively; in pyramidality, the difference is 1° on average and 6° at most (for 10c). Structural features such as planar, trans-bent, and twisted do not depend on the level of calculation, except for 1c and 2c. The optimized structures of 1c and 2c at the MP2/6-311+G(3df,2p) level are planar, while those at the MP2/6-311++G(d,p) level are slightly trans-bent.
-
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42
-
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0037554023
-
-
note
-
The average difference in relative stabilities between the results of both calculations for compounds 1-12 is 0.5 kcal/mol. The dominant isomer is the same, independent of the level of calculation, except for 3. In the case of compound 3, the cis isomer is more stable than the trans isomer by 0.6 kcal/mol at the MP2/6-31H+G(3df,2p) level, while the trans isomer is more stable than the cis isomer by 2.2 kcal/mol at the MP2/6-311++G(d,p) level. The 6-311+G(3df,2p) basis contains high-exponent d and f functions, but it does not contain a diffuse function on hydrogen which is included in the 6-311++G(d,p) basis. To check the effects of the diffuse function, single-point calculations were performed using the basis sets with both high-exponent d and f functions and the diffuse function on hydrogen (MP2/6-311++G(3df,-2p)) at the MP2/6-311+G(3df,2p) geometry of 3. The calculation shows that the trans isomer is more stable by 2.1 kcal/mol. The result demonstrates that the diffuse function on hydrogen atoms is important for the energetics of 3.
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