Theoretical studies on the stability of N-methylformamide in both liquid and gas phases

Ab initio (restricted Hartree–Fock and DFT) and molecular mechanics calculations at MM2 level were performed for N-methylformamide (NMF) molecule and for three dimers in order to investigate the relative stability of the cis and trans conformers. The ab initio calculations show that no intramolecular interaction is relevant for the stability of the conformers explored. The trans conformer is the most stable. The MM calculations revealed that a double H-bonded cyclic cis–cis dimer is the most stable among the studied dimers, followed by a ‘linear’ H-bonded trans–trans dimer. This ‘linear’ dimer, however, is prevalent in the liquid phase.