Dynamic NMR: comparison of the experimental barriers to internal rotation in N,N-dimethylformamide with those calculated by the ab initio SCF MO method

Abstract

The GAUSSIAN 70 package of ab initio computer programs has been used to determine the total energies, force constants and dipole moments of the ground and transition states of DMF following complete geometry optimisation. The 4–31G split-valence basis set was employed. There is good agreement between the resulting geometry and that determined by electron diffraction. The barriers to internal rotation about the CN amide and NMe bonds so derived are compared with those determined experimentally by NMR methods.