Determination of the intermolecular potential energy surface for (HCl)2 from vibration--rotation--tunneling spectra.
An accurate and detailed semiempirical intermolecular potential energy surface for (HCl)2 has been determined by a direct nonlinear least-squares fit to 33 microwave, far-infrared and near-infrared spectroscopic quantities using the analytical potential model of Bunker et al. [J. Mol. Spectrosc. 146, 200  (l99l)] and a rigorous four-dimensional dynamical method (described in the accompanying paper). The global minimum (De= -692 cm-1) is located near the hydrogen-bonded L-shaped geometry (R=3.746 angstroms, theta1=9 degrees, theta2=89.8 degrees, and phi=180 degrees). The marked influence of anisotropic repulsive forces is evidenced in the radial dependence of the donor-acceptor interchange tunneling pathway. The minimum energy pathway in this low barrier (48 cm-1) process involves a contraction of 0.1 angstroms in the center of mass distance (R) at the C2h symmetry barrier position. The new surface is much more accurate than either the ab initio formulation of Bunker et al. or a previous semiempirical surface [J. Chem. Phys. 78, 6841 (1983)].
Elrod
M J
MJ
Department of Chemistry, University of California, Berkeley 94720, USA.
Saykally
R J
RJ
D002627:Chemistry, Physical / Q000379:methods*; D006851:Hydrochloric Acid / Q000737:chemistry*; D006860:Hydrogen Bonding; D016018:Least-Squares Analysis; D008433:Mathematics; D008958:Models, Molecular; D015394:Molecular Structure; D012399:Rotation; D013055:Spectrophotometry, Infrared / Q000379:methods*; D017550:Spectroscopy, Fourier Transform Infrared / Q000379:methods; D019265:Spectroscopy, Near-Infrared / Q000379:methods; D055672:Static Electricity; D014732:Vibration
D006851:Hydrochloric Acid