Journal of Physical Chemistry A, Vol.112, No.51, 13393-13401, 2008
Spectroscopic Identification of Higher-Order Rare Gas-Dihalogen Complexes with Different Geometries: He-2,He-3 center dot center dot center dot Br-2 and He-2,He-3 center dot center dot center dot ICl
Rovibronic transitions of multiple conformers of the He-2 center dot center dot center dot Br-79(2)(X, v '' = 0), He-3 center dot center dot center dot Br-79(2)(X, v '' = 0), He-2 center dot center dot center dot(ICl)-Cl-35(X, v '' = 0), and He-3 center dot center dot center dot(ICl)-Cl-35(X, v '' = 0) complexes stabilized in a pulsed, supersonic expansion are observed in action spectra recorded in the B-X region of the dihalogens. In addition to features associated with He-2 center dot center dot center dot Br-79(2) and He-2 center dot center dot center dot(ICl)-Cl-35 complexes with the rare gas atoms localized in the toroidal potential well lying in a plane perpendicular to the dihalogen bond, those associated with a ground-state conformer that has one He atom localized in the toroidal potential and the other He atom localized in the linear well at the end of the dihalogen moiety are also identified. Transitions of at least three conformers of the He-3 center dot center dot center dot Br-2 complex and two conformers of the He-3 center dot center dot center dot ICl complex are also observed. The relative populations of the different conformers are found to depend on where along the supersonic expansion the spectra are recorded, and thus on the local temperature regime sampled. The He-2 center dot center dot center dot Br-79(2) and He-2 center dot center dot center dot(ICl)-Cl-35 conformers with one He atom in each well are found to be the more stable conformers.