Laser-induced fluorescence and action spectroscopy experiments have identified multiple conformers of the D2 ⋯ ICl van der Waals complex for both ortho-D2 (o-D2) and para-D2 (p-D2). As with die analogous H2 ⋯ ICl van der Waals complexes [Darr, J. P.; Crowther, A. C.; Loomis, R. A.; Ray, S. E.; McCoy, A. B. J. Phys. Chem. A 2007, 111, 13387], the C2v conformer with the deuterium molecule localized at the iodine atom end of the dihalogen is significantly more stable than the asymmetric conformer that has the deuterium positioned orthogonally to the ICl bond axis, D0″ = 223.9(2.4) versus 97.3(8)-103.9(3) cm-1 for p-D2⋯I 35CI(X,v″ = 0). For both conformers, complexes containing p-D2 are found to be more strongly bound than those with o-D 2. The electronically excited D2⋯ICl(A,v′) and D2⋯ICl(B,v′) complexes are found to have equilibrium geometries that are nearly the same as those of the ground-state asymmetric structures. Calculated D2⋯ICl(B,v′=3) energies and probability amplitudes obtained using a simple scaled He + ICl(B,v′=3) potential provide clues to the nature of the different excited-state levels accessed.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry