A Theoretical Study of the Conformational Changes in Hydrazine

Abstract

Abinitio restricted Hartree–Fock–Roothaan l.c.a.o.–m.o.–s.c.f. calculations using a Gaussian lobe basis with bond functions have been performed to determine the characteristics of the potential surface for nuclear motions in hydrazine. It was found that in its equilibrium conformation the molecule has a dihedral angle of 95°. The barrier to pyramidal inversion at one nitrogen is 6.1 kcal/mol and the syn and anti rotational barriers are calculated to be 12.0 and 1.6 kcal/mol, respectively. There is a very slight torsional component in the inversion pathway. During rotation over the anti barrier the bond angles contract from their average equilibrium value of 109.5° to 105.3°. This contraction appears to be an important feature of the rotational potential curve. Features of the surface are used to rationalize experimental results in cyclic and acyclic substituted hydrazines.