title: Density functional theory study of self-association of N-methylformamide and its effect on intramolecular and intermolecular geometrical parameters and the cis/trans population.
abstract: The single-point total energy (E) of several acyclic and cyclic oligomers of N-methylformamide (NMF) was computed by the first time without any geometrical restriction, using the B3LYP6-31G* method of the density functional theory in order to determine the effect of self-association on intramolecular geometrical parameters of cis- and trans-NMF, the intermolecular distances of the hydrogen-bonding chains formed by NMF as well as intermolecular association energies including counterpoise corrections. It is concluded that liquid NMF exists mainly as polymers formed by self-association of trans-NMF units, whereas the cis-NMF isomer occurs as isolated units inserted along the chains. These computational results are in accordance with the experimentally determined predominance (ca. 90%) of trans-NMF population by means of (1)H- NMR and other spectroscopic techniques, but in severe contradiction with a recent interpretation of x-ray diffraction data on liquid NMF, postulating a cyclic trimer of cis-NMF (c-C(3)) as the predominating species. The counterpoise-corrected values of the association energy, DeltaE(CP), calculated for cyclic oligomers, increase with the polymerization degree (n) revealing a high grade of cooperative effect for amidic hydrogen-bonded chains. Noteworthy, the difference between the DeltaE(CP) values of the cyclic cis- and trans-homooligomers of NMF is positive for n=2 and 3 but negative for n > or =4.
authors.affiliation: Departamento de Química Orgánica, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, Avenida Complutense s/n, E-28040 Madrid, Spain. agamar@quim.ucm.es
authors.forename: A
authors.initials: A
authors.lastname: García Martínez
authors.forename: E
authors.initials: E
authors.lastname: Teso Vilar
authors.forename: A
authors.initials: A
authors.lastname: García Fraile
authors.forename: P
authors.initials: P
authors.lastname: Martínez-Ruiz