Probing the dependence of long-range, four-atom interactions on intermolecular orientation: 3. Hydrogen and iodine.

Two-laser, action spectroscopy experiments have been performed in the I(2)B-X, υ'-0 spectral region on H(2)···I(2) and D(2)···I(2) complexes to investigate the dependence of the H(2)/D(2) + I(2) intermolecular interactions on orientation. The spectra contain features associated with at least two different conformers of the ground-state H(2)/D(2)···I(2)(X,υ'' = 0) complexes; one conformer has a preferred T-shaped geometry with the H(2)/D(2) moiety localized in a potential minimum that is orthogonal to the I-I bond axis, and the second conformer has a linear geometry with the H(2)/D(2) moiety positioned in minima at either end of the I(2) molecule, along the bond axis. Those features associated with complexes containing para-H(2)(j = 0), ortho-H(2)(j = 1), ortho-D(2)(j = 0), and para-D(2)(j = 1) are also assigned. The linear conformers are found to be more strongly bound than the T-shaped conformers with binding energies of 118.9(1.9) cm(-1) versus 91.3-93.3 cm(-1) for the ortho-H(2)···I(2) complexes and 144.2(2.1) cm(-1) versus 107.9 cm(-1) for the para-D(2)···I(2) complexes, respectively. Electronic structure calculations of the complexes containing ICl and I(2) with H(2), He, Ne, and Ar were performed to reveal the nature of the interactions and to shed insight into the origins of the different binding energies. The most stable minima in the H(2)/D(2) + I(2)(B,υ') excited-state potentials have T-shaped geometries. Calculated energies and probability amplitudes of the excited-state levels provide insight into the different excited-state intermolecular vibrational levels accessed by transitions of the two ground-state conformers.