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Ab initio potential-energy surface for the reaction Ca+HCl --> CaCl+H

AutorVerbockhaven, Gilles; Sanz, Cristina; Groenenboom, Gerrit C.; Roncero, Octavio ; Avoird, Ad van der
Palabras claveAb initio calculations
Potential energy surfaces
Hydrogen compounds
Ground states
Molecular electronic states
Molecular configurations
Configuration interactions
van der Waals forces
Coupled cluster calculations
Infrared spectra
Rotational-vibrational states
[PACS] Ab initio calculations (atoms and molecules)
[PACS] Potential energy surfaces for chemical reactions
[PACS] General molecular conformation and symmetry; stereochemistry
[PACS] Intermolecular and atom–molecule potentials and forces
[PACS] Coupled cluster theory (atoms and molecules)
[PACS] Infrared molecular spectra
[PACS] Vibration-rotation analysis (molecular spectra)
Fecha de publicación23-may-2005
EditorAmerican Institute of Physics
CitaciónJournal of Chemical Physics 122(20): 204307 (2005)
ResumenThe potential-energy surface of the ground electronic state of CaHCl has been obtained from 6400 ab initio points calculated at the multireference configuration-interaction level and represented by a global analytical fit. The Ca+HCl --> CaCl+H reaction is endothermic by 5100 cm–1 with a barrier of 4470 cm–1 at bent geometry, taking the zero energy in the Ca+HCl asymptote. On both sides of this barrier are potential wells at linear geometries, a shallow one due to van der Waals interactions in the entrance channel, and a deep one attributed to the H(–)Ca(++)Cl(–) ionic configuration. The accuracy of the van der Waals well depth, ≈ 200 cm–1, was checked by means of additional calculations at the coupled-cluster singles and doubles with perturbative triples level and it was concluded that previous empirical estimates are unrealistic. Also, the electric dipole function was calculated, analytically fitted in the regions of the two wells, and used to analyze the charge shifts along the reaction path. In the insertion well, 16 800 cm–1 deep, the electric dipole function confirmed the ionic structure of the HCaCl complex and served to estimate effective atomic charges. Finally, bound rovibrational levels were computed both in the van der Waals well and in the insertion well, and the infrared-absorption spectrum of the insertion complex was simulated in order to facilitate its detection.
Descripción12 pages, 9 figures, 7 tables.-- PACS nrs.: 31.15.Ar; 82.20.Kh; 33.15.Bh; 34.20.Gj; 31.15.Dv; 33.20.Ea; 33.20.Vq.
Versión del editorhttp://dx.doi.org/10.1063/1.1899154
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