Infrared light on molecule-molecule and molecule-surface collisions

By analyzing measured infrared absorption of pure CH4 gas under both "free" (large sample cell) and "confined" (inside the pores of a silica xerogel sample) conditions we give a demonstration that molecule-molecule and molecule-surface collisions lead to very different propensity rules for rotational-state changes. Whereas the efficiency of collisions to change the rotational state (observed through the broadening of the absorption lines) decreases with increasing rotational quantum number J for CH4-CH4 interactions, CH4-surface collisions lead to J-independent linewidths. In the former case, some (weak) collisions are inefficient whereas, in the latter case, a single collision is sufficient to remove the molecule from its initial rotational level. Furthermore, although some gas-phase collisions leave J unchanged and only modify the angular momentum orientation and/or symmetry of the level (as observed through the spectral effects of line mixing), this is not the case for the molecule-surface collisions since they always change J (in the studied J=0-14 range).

Accurate ground-state potential energy surfaces of the C2H2–Kr and C2H2–Xe van der Waals complexes

Accurate ab initio intermolecular potential energy surfaces (IPES) have been obtained for the first time for the ground electronic state of the C 2H2-Kr and C2H2-Xe van der Waals complexes. Extensive tests, including complete basis set and all-electron scalar relativistic results, support their calculation at the CCSD(T) level of theory, using small-core relativistic pseudopotentials for the rare-gas atoms and aug-cc-pVQZ basis sets extended with a set of 3s3p2d1f1g mid-bond functions. All results are corrected for the basis set superposition error. The importance of the scalar relativistic and rare-gas outer-core (n.1)d correlation effects is investigated. The calculated IPES, adjusted to analytical functions, are characterized by global minima corresponding to skew T-shaped geometries, in which the Jacobi vector positioning the rare-gas atom with respect to the center of mass of the C2H2 moiety corresponds to distances of 4.064 and 4.229Å, and angles of 65.22° and 68.67° for C 2H2-Kr and C2H2-Xe, respectively. The interaction energy of both complexes is estimated to be -151.88 (1.817 kJ mol-1) and -182.76 cm-1 (2.186 kJ mol-1), respectively. The evolution of the topology of the IPES as a function of the rare-gas atom, from He to Xe, is also discussed. © 2012 Taylor and Francis.