Structure and Dynamics of the Aniline−Argon Complex as Derived from its Potential Energy Surface

The structure and dynamics of the van der Waals (vdW) complex of aniline (An) with argon (Ar) are studied
using ab initio methods. The inversion potential of the aniline−argon (AnAr) complex perturbed by the weak
vdW interaction is calculated taking into account subtle corrections from the zero-point energy of the vdW
modes and from the frequency shifts of the An normal modes modified by the complexation. The intermolecular
potential energy surface (PES) of the AnAr complex is determined by performing a large-scale computation
of the interaction energy and the fitting of the analytical many-body expansion to the set of single-point
interaction energies. The PES determined shows two deep local minima corresponding to the anti and syn
AnAr conformers. The difference in the energies of these two minima is only 15 cm-1, but it is sufficient to
localize the inversion wave functions and to form the two conformers. In the conformer anti (syn) of lower
(higher) energy, Ar is bound to the An ring opposite (adjacent) the amino-hydrogens. In the additional local
minima higher in energy, Ar approaches the aniline ring between the C−H bonds near its plane. An additional
local minimum is located opposite of nitrogen between the two N−H bonds. The high-energy minima are,
however, too flat to form stable conformers. The perturbation of the interaction of Ar with the phenyl ring
by the NH2 group is described by the vdW hole, which is responsible for unusually strong intermode mixing
in the excited intermolecular vibrational states. The analysis of these states calculated for the ground (S0) as
well as the first excited electronic state (S1) resolves difficulties faced earlier with the assignment of the
observed vibronic bands of AnAr.