R. Vargas et al., Strength of the N-H center dot center dot center dot O=C and C-H center dot center dot center dot O=C bonds in formamide and N-methylacetamide dimers, J PHYS CH A, 105(20), 2001, pp. 4963-4968
The structures of the dimers of formamide and N-methylacetamide have been c
alculated at the ab initio electronic structure theory level, second-order
Moller-Plesset perturbation theory (MP2) with augmented correlation consist
ent basis sets. Five unique structures were optimized for the formamide dim
ers at the MP2/ aug-cc-pVDZ and MP2/aug-cc-pVTZ levels. At the optimized ge
ometries obtained with the aug-cc-pVTZ basis set, MP2 energies were evaluat
ed with the aug-cc-pVQZ basis set, allowing an extrapolation of the energie
s to the complete basis set limit. Four structures were found for the N-met
hylacetamide dimer at the MP2/aug-cc-pVDZ level, and single-point energies
were calculated at the MP2/aug-cc-pVTZ level. In both systems, the basis se
t superposition error was estimated with the counterpoise method. The stren
gth of the N-H O-...=C bond has a mean value of 7.1 kcal/mol in the formami
de dimers and a mean value of 8.6 kcal/mol in the N-methylacetamide dimers.
The difference in hydrogen bond strengths is attributed to differences in
basicity at the carbonyl oxygen receptor site. In several dimers C-(HO)-O-.
..=C hydrogen bonds play an important role in stabilizing these intermolecu
lar complexes, increasing the interaction energy by 1.1-2.6 kcal/mol per in
teraction.