Fully dimensional ab initio description of the structure and energetics of azabenzene-argon complexes.
The structure and energetics of van der Waals complexes of argon with azabenzenes: pyridine, pyrazine, pyrimidine, pyridazine, s-triazine, and s-tetrazine are studied using the second-order Moller-Plesset perturbation theory combined with well-balanced basis sets. The full optimization of the cluster structures and computation of the inter- and intramolecular vibrational frequencies is performed by eliminating the basis set superposition error. The argon equilibrium coordinates are calculated with the accuracy comparable to that reached by standard methods of the structure determination from the spectral data. A simple rule to predict the position of argon with respect to the geometric center of the azabenzene ring is found. The calculated harmonic frequencies of the intermolecular vibrational modes are scaled by the factor of 0.85 to eliminate systematic errors coming from the neglect of anharmonic effects. The scaled frequencies agree with the experimental ones to about 1 cm(-1), except for pyrimidine-argon and tetrazine-argon for which empirical fundamental frequency estimates are problematic. A simple relation connecting the intermolecular bending frequencies and the monomer quadrupole tensor is found. The perturbation of the monomer properties caused by complexation is analyzed. The modification of the monomer structure by the interaction with argon and its influence on the binding energy appears to be negligible in all complexes studied. However, this interaction affects appreciably the intramolecular modes and causes their frequency shifts. As a consequence, the dissociation energy of the complexes increases by about 5 cm(-1).
Makarewicz
Jan
J
Faculty of Chemistry, Adam Mickiewicz University, Grunwaldzka 6, PL 60-780 Poznań, Poland. jasiu@rovib.amu.edu.pl