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A reviewer noted the large difference in the calculation of the energy (6 kcal/mol for the gas phase) between 9 and 20 in Scheme 4. Previous studies indicate the structurally related 2-formylpyridine has an s-trans to s-cis free energy difference of 2 kcal/mol in solution and 7 kcal/mol in the gas phase. Furthermore, the coordination of the carbonyl oxygen can be expected to polarize the carbonyl group, making the energy difference between the s-trans and s-cis conformers larger.
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A reviewer noted the large difference in the calculation of the energy (6 kcal/mol for the gas phase) between 9 and 20 in Scheme 4. Previous studies indicate the structurally related 2-formylpyridine has an s-trans to s-cis free energy difference of 2 kcal/mol in solution and 7 kcal/mol in the gas phase." Furthermore, the coordination of the carbonyl oxygen can be expected to polarize the carbonyl group, making the energy difference between the s-trans and s-cis conformers larger.
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The 6-31G(d′) basis set has the exponent for the d polarization function for C, O, and N taken from the 6-311G(d) basis sets, instead of the original arbitrarily assigned value of 0.8 used in the 6-31G(d) basis sets.
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The 6-31G(d′) basis set has the exponent for the d polarization function for C, O, and N taken from the 6-311G(d) basis sets, instead of the original arbitrarily assigned value of 0.8 used in the 6-31G(d) basis sets.
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