Potential-energy surface, dynamics of van der Waals motions, and vibronic transitions in p-difluorobenzene-argon complex.
The dynamics of van der Waals vibrational motions and vibronic spectrum of the complex of argon with p-difluorobenzene (ArDFB) are investigated using the ab initio method. The electronic ground-state potential-energy surface of the complex is calculated at the second-order Møller-Plesset level of theory using a well-balanced basis set aug-cc-pVDZ and its reduced version without tight polarization functions. The dissociation energy of 351 cm(-1) and the binding energy of 402 cm(-1) determined at the Ar distance of 3.521 Angstroms from the DFB ring well agree with the experimental data available. The character of calculated vibrational levels is analyzed and the effect of a strong coupling between the stretching and bending motions is investigated. A new class of hybrid states created by this coupling is found. To investigate the vibronic S(1)-S(0) spectrum, the surfaces of the electronic transition dipole moment are calculated using the ab initio method. From these surfaces, the vibronic transition intensities are determined and employed to assign the Franck-Condon- and Herzberg-Teller-induced transitions.
Makarewicz
Jan
J
Faculty of Chemistry, Adam Mickiewicz University, Poznań, Poland. amandanici@unime.it