Abstract
The structural stability and internal rotations in cyclopropanecarboxylic acid and cyclopropanecarboxamide were investigated by the DFT-B3LYP and the ab initio MP2 calculations using 6-311G** and 6-311+G** basis sets. The computations were extended to the MP4//MP2/6-311G** and CCSD(T)//MP2/6-311G** single-point calculations. From the calculations the molecules were predicted to exist predominantly in the cis (C=O group eclipses the cyclopropane ring) with a cis-trans barrier of about 4-6 kcal/mol. The CCOH torsional barrier in the acid was estimated to be about 12-13 kcal/mol while the corresponding OCNH torsional barrier in the amide was calculated to be about 20 kcal/mol. The equilibrium constant k for the cis double left right arrow trans interconversion in cyclopropanecarboxylic acid was calculated to be 0.1729 at 298.15 K that corresponds to an equilibrium mixture of about 85% cis and 15% trans. The vibrational frequencies were computed at the DFT-B3LYP level. Normal coordinate calculations were carried out and potential energy distributions were calculated for the low energy cis conformer of the molecules. Complete vibrational assignments were made on the basis of normal coordinate calculations and comparison with experimental data of the molecules. (C) 2008 Elsevier B.V. All rights reserved.