Acetamide, a challenge to theory and experiment? On the molecular structure, conformation, potential to internal rotation of the methyl group and force fields of free acetamide as studied by quantum chemical calculations

Abstract

The molecular geometry has been optimized without any constraints using different basis sets and levels of theory as: Hartree-Fock with basis sets 6–31+G∗∗, 6–311++G∗∗, cc-pVTZ and aug-cc-pVTZ, MP2 with basis sets 6–311++G∗∗ and cc-pVTZ, MP3 with basis set 6–311++G∗∗, and density functional theory with basis sets 6–311++G∗∗ and cc-pVTZ. Small basis sets up to 6-31G predict the syn conformation of the methyl group to be the most stable conformation. Larger basis sets predict an unsymmetrical conformation with one of the H atoms perpendicular to the amide skeleton or an anti-like conformation. Dunnings correlation consistent polarized valence triple zeta, cc-pVTZ, basis set including MP2 predict two conformations, one perpendicular and one anti to be the most stable. The DFT calculations predict anti-like conformations. The most accurate calculations predict anti-like conformations which have not been predicted previously. The vibrational frequencies have been calculated for several basis sets and compared to the observed frequencies. The wagging frequency of the NH 2 is very dependent on the basis sets and levels of theory. Most calculations predict a planar NH 2 group in agreement with experiment. A scaled molecular force field has been determined by fitting the calculated frequencies to the observed ones for the perpendicular conformation using MP2/cc-pVTZ. The barrier heights for the methyl group have been calculated. The rotational constants, I A + I B − I C values and dipole moments are compared with experimental values.