Near-resonant rotational energy transfer in HCl–H{sub 2} inelastic collisions

Journal Article · Fri Feb 14 00:00:00 EST 2014 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4864359· OSTI ID:22255112

Lanza, Mathieu; Lique, François ^[1]; Kalugina, Yulia ^[1]; Wiesenfeld, Laurent ^[2]

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1. LOMC - UMR 6294, CNRS-Université du Havre, 25 rue Philippe Lebon, BP 540, 76058 Le Havre (France)
2. UJF-Grenoble 1/CNRS, Institut de Planétologie et d'Astrophysique de Grenoble (IPAG) UMR 5274, Grenoble F-38041 (France)

We present a new four-dimensional (4D) potential energy surface for the HCl–H{sub 2} van der Waals system. Both molecules were treated as rigid rotors. Potential energy surface was obtained from electronic structure calculations using a coupled cluster with single, double, and perturbative triple excitations method. The four atoms were described using the augmented correlation-consistent quadruple zeta basis set and bond functions were placed at mid-distance between the HCl and H{sub 2} centers of mass for a better description of the van der Waals interaction. The global minimum is characterized by the well depth of 213.38 cm{sup −1} corresponding to the T-shape structure with H{sub 2} molecule on the H side of the HCl molecule. The dissociation energies D{sub 0} are 34.7 cm{sup −1} and 42.3 cm{sup −1} for the complex with para- and ortho-H{sub 2}, respectively. These theoretical results obtained using our new PES are in good agreement with experimental values [D. T. Anderson, M. Schuder, and D. J. Nesbitt, Chem. Phys. 239, 253 (1998)]. Close coupling calculations of the inelastic integral rotational cross sections of HCl in collisions with para-H{sub 2} and ortho-H{sub 2} were performed at low and intermediate collisional energies. Significant differences exist between para- and ortho-H{sub 2} results. The strongest collision-induced rotational HCl transitions are the transitions with Δj = 1 for collisions with both para-H{sub 2} and ortho-H{sub 2}. Rotational relaxation of HCl in collision with para-H{sub 2} in the rotationally excited states j = 2 is dominated by near-resonant energy transfer.

• OSTI ID: 22255112
• Journal Information: Journal of Chemical Physics, Vol. 140, Issue 6; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
COLLISIONS
CROSS SECTIONS
DISSOCIATION ENERGY
ELECTRONIC STRUCTURE
ENERGY TRANSFER
EXCITATION
EXCITED STATES
FOUR-DIMENSIONAL CALCULATIONS
HYDROCHLORIC ACID
HYDROGEN
INTERACTIONS
MOLECULES
POTENTIAL ENERGY
SURFACES
VAN DER WAALS FORCES