caa a22 4500 378913611 CHVBK 20180305123547.0 cr unu---uuuuu 161128e20040401xx s 000 0 eng 10.1524/zpch.218.4.377.29196 doi (NATIONALLICENCE)gruyter-10.1524/zpch.218.4.377.29196 Cationic Van-der-Waals Complexes: Theoretical Study of Ar2H+ Structure and Stability [Elektronische Daten] [Thomas Ritschel, Lutz Zülicke, Philip J. Kuntz] The electronic and geometric structure, stability and molecular properties of the cationic van-der-Waals complex Ar2H+ in its ground electronic state are studied by means of two ab-initio quantum-chemical approaches: conventional configuration interaction (multi-reference and coupled-cluster methods) and a diatomics-in-molecules model with ab-initio input data. To ensure consistency between the two approaches, one and the same one-electron atomic basis set (aug-cc-pVTZ by Dunning) is employed in both. The topography of the ground-state potential-energy surface is examined with respect to the nature of the binding and the stability of structures corresponding to stationary points. In accordance with most earlier theoretical work, there are two local minima at linear arrangements: a strongly bound centro-symmetric moiety, (Ar-H-Ar)+, and a weakly bound van-der-Waals complex, Ar···ArH+. These are separated by a low barrier. Only the centro-symmetric molecule is significantly stable (De = 0.68eV) against fragmentation into Ar + ArH+ and should have structural and dynamical relevance. A fairly simple diatomics-in-molecules model taking into account only the few lowest electronic fragment states yields a qualitatively correct description of the ground state but shows quantitative deviations from the more accurate configuration-interaction data in detail. Nevertheless, it should provide a good starting point for the treatment of larger complexes ArnH+ with n > 2. © 2004 Oldenbourg Wissenschaftsverlag GmbH Thermodynamics & statistical physics nationallicence Laboratory techniques, experiments nationallicence Physical chemistry nationallicence Ritschel Thomas aut Zülicke Lutz aut Kuntz Philip J. aut Zeitschrift für Physikalische Chemie/International journal of research in physical chemistry and chemical physics Oldenbourg Wissenschaftsverlag GmbH 218/4/2004(2004-04-01), 377-390 0942-9352 218:4/2004<377 2004 218 zpch https://doi.org/10.1524/zpch.218.4.377.29196 text/html Onlinezugriff via DOI 1 research article jats NATIONALLICENCE 856 40 https://doi.org/10.1524/zpch.218.4.377.29196 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Ritschel Thomas aut NATIONALLICENCE 700 1- Zülicke Lutz aut NATIONALLICENCE 700 1- Kuntz Philip J. aut NATIONALLICENCE 773 0- Zeitschrift für Physikalische Chemie/International journal of research in physical chemistry and chemical physics Oldenbourg Wissenschaftsverlag GmbH 218/4/2004(2004-04-01), 377-390 0942-9352 218:4/2004<377 2004 218 zpch CC0 http://creativecommons.org/publicdomain/zero/1.0 nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-gruyter