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dc.contributor.authorVerbockhaven, Gilles-
dc.contributor.authorSanz, Cristina-
dc.contributor.authorGroenenboom, Gerrit C.-
dc.contributor.authorRoncero, Octavio-
dc.contributor.authorAvoird, Ad van der-
dc.identifier.citationJournal of Chemical Physics 122(20): 204307 (2005)en_US
dc.description12 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.en_US
dc.description.abstractThe 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.en_US
dc.description.sponsorshipThis work has been supported by MCYT (Spain), under Grant No. BFM2001-2179, and by the European Research Training Network THEONET II.en_US
dc.format.extent209679 bytes-
dc.publisherAmerican Institute of Physicsen_US
dc.subjectAb initio calculationsen_US
dc.subjectPotential energy surfacesen_US
dc.subjectHydrogen compoundsen_US
dc.subjectGround statesen_US
dc.subjectMolecular electronic statesen_US
dc.subjectMolecular configurationsen_US
dc.subjectConfiguration interactionsen_US
dc.subjectvan der Waals forcesen_US
dc.subjectCoupled cluster calculationsen_US
dc.subjectInfrared spectraen_US
dc.subjectRotational-vibrational statesen_US
dc.subject[PACS] Ab initio calculations (atoms and molecules)en_US
dc.subject[PACS] Potential energy surfaces for chemical reactionsen_US
dc.subject[PACS] General molecular conformation and symmetry; stereochemistryen_US
dc.subject[PACS] Intermolecular and atom–molecule potentials and forcesen_US
dc.subject[PACS] Coupled cluster theory (atoms and molecules)en_US
dc.subject[PACS] Infrared molecular spectraen_US
dc.subject[PACS] Vibration-rotation analysis (molecular spectra)en_US
dc.titleAb initio potential-energy surface for the reaction Ca+HCl --> CaCl+Hen_US
dc.description.peerreviewedPeer revieweden_US
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