Probing the dependence of long-range, four-atom interactions on intermolecular orientation. 1. Molecular hydrogen and iodine monochloride.

The dependence of the long-range interactions between molecular hydrogen and iodine monochloride on the geometry between the molecules is investigated. Laser-induced fluorescence and action spectroscopy experiments have identified multiple conformers of the o,p-H2...I35,37Cl(X,v' '=0) van der Waals complexes. A conformer with the hydrogen molecule localized at the iodine end of the dihalogen, most likely with C2v symmetry, is significantly more stable than an asymmetric conformer with the hydrogen localized in the well oriented orthogonally to the I-Cl bond axis, D0' ' = 186.4(3) cm-1 versus 82.8(3)

Experimental and theoretical investigations of the He...I2 rovibronic spectra in the I2 B-X, 20-0 region.

The laser-induced fluorescence and action spectra of I2 in a helium supersonic expansion have been recorded in the I2 B-X, 20-0 region. Two features are identified within the spectra. The lower-energy feature arises from transitions between states that are localized in a T-shaped conformation on both the X- and B-state potentials. The higher-energy feature reflects transitions from states that are localized in a linear conformation on the X state to states that have energies that are larger than the barrier for free rotation of the rare gas atom about the I2 molecule on the B-state potential. Ground-state binding energies of 16.6(6) and 16.3(6) cm-1 were determined for the T-shaped and linear conformers, respectively. These spectra are compared to those calculated using the experimentally determined rotational temperatures. Based on the agreement between the experimental and calculated spectra, the binding energies of the J'=0 states with 0 and 2-6 quanta of excitation in the He...I2 bending mode on the B state were determined. Several models for the B-state potential were used to investigate the origins of the shape of the contour of the higher-energy feature in the spectra for He...I2 and He...Br2. The shape of the contours was found to be relatively insensitive to the choice of potential. This leads us to believe that the spectra of these systems are relatively insensitive to the parameters of the B-state potential energy surface and are more sensitive to properties of the halogen molecule.

Stabilization and rovibronic spectra of the T-shaped and linear ground-state conformers of a weakly bound rare-gas-homonuclear dihalogen complex: He...Br2.

Laser-induced fluorescence spectra of Br(2) entrained in a He supersonic expansion have been recorded in the Br(2) B-X, 8-0, 12-0, and 21-0 spectral regions at varying downstream distances, and thus different temperature regimes. Features associated with transitions of the T-shaped and linear He...Br(2)(X,nu(") = 0) complexes are identified. The changes in the relative intensities of the T-shaped and linear features with cooling in the expansion indicate that the linear conformer is energetically more stable than the T-shaped conformer. A He + Br(2)(X,nu(") = 0) ab initio potential-energy surface, computed at the coupled cluster level of theory with a large, flexible basis set, is used to calculate the binding energies of the two conformers, 15.8 and 16.5 cm(-1) for the T-shaped and linear complexes, respectively. This potential and an excited-state potential [M. P. de Lara-Castells, A. A. Buchachenko, G. Delgado-Barrio, and P. Villareal, J. Chem. Phys. 120, 2182 (2004)] are used to calculate the excitation spectra of He...(79)Br(2)(X,nu(") = 0) in the Br(2) B-X, 12-0 region. The calculated spectra are used to make spectral assignments and to determine the energies of the excited-state intermolecular vibrational levels accessed in the observed transitions. Temperature-dependent laser-induced fluorescence spectra and a simple thermodynamic model [D. S. Boucher, J. P. Darr, M. D. Bradke, R. A. Loomis, and A. B. McCoy, Phys. Chem. Chem. Phys. 6, 5275 (2004)] are used to estimate that the linear conformer is 0.4(2) cm(-1) more strongly bound than the T-shaped conformer. Two-laser action spectroscopy experiments reveal that the binding energy of the linear He...(79)Br(2)(X,nu(") = 0) conformer is 17.0(8) cm(-1), and that of the T-shaped He...(79)Br(2)(X,nu(") = 0) conformer is then 16.6(8) cm(-1), in good agreement with the calculated values.