EXPERIMENTAL AND THEORETICAL-STUDY OF 1-CYANONAPHTHALENE CLUSTERED WITH ACETONITRILE AND WATER IN A SUPERSONIC JET

Laser-induced fluorescence excitation spectra of 1- and 2-cyanonaphthalene/acetonitrile complexes and 1-cyanonaphthalene/water(n) (n = 1,3) clusters together with the mixed 1-cyanonaphthalene/water/acetonitrile trimer have been investigated. The experimental data have been interpreted by calculating the binding energy and the equilibrium geometry for the clusters, by means of the exchange perturbation method of Claverie. The calculated geometry of the complexes is planar and involves a strong specific interaction, mainly electrostatic, involving a hydrogen atom and an electronegative atom. In all the cases understudy, the calculation reproduces satisfactorily the number of isomers observed in the excitation spectrum and the shift of their electronic transition relative to that of the uncomplexed molecule. The energy barrier between isomers and the geometry of the saddle point have been determined. The calculated value compares with that measured for the isomerization process observed in the excited 1-cyanonaphthalene/acetonitrile complex.