Experimental and theoretical studies of the CN-Ar van der Waals complex

摘要

The CN-Ar van der Waals complex has been observed using the B (2)Sigma(+)-X (2)Sigma(+) and A (2)Pi-X (2)Sigma(+) electronic transitions. The spectra yield a dissociation energy of D-0"=102 +/- 2 cm(-1) and a zero-point rotational constant of B-0"=0.067 +/- 0.005 cm(-1) for CN(X)-Ar. The dissociation energy for CN(A)-Ar was found to be D-0'=125 +/- 2 cm(-1). Transitions to vibrationally excited levels of CN(B)-Ar dominated the B-X spectrum, indicative of substantial differences in the intermolecular potential energy surfaces (PESs) for the X and B states. Ab initio PESs were calculated for the X and B states. These were used to predict rovibrational energy levels and van der Waals bond energies (D-0'=115 and D-0'=183 cm(-1)). The results for the X state were in reasonably good agreement with the experimental data. Spectral simulations based on the ab initio potentials yielded qualitative insights concerning the B-X spectrum, but the level of agreement was not sufficient to permit vibronic assignment. Electronic predissociation was observed for both CN(A)-Ar and CN(B)-Ar. The process leading to the production of CN(A,nu=8,9) fragments from the predissociation of CN(B,nu=0)-Ar was characterized using time-resolved fluorescence and optical-optical double resonance measurements. (c) 2008 American Institute of Physics.