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Comparison of the experimental, semi-experimental and ab initio equilibrium structures of acetylene: influence of relativistic effects and of the diagonal Born-Oppenheimer corrections.

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Liévin, J. [Université Libre de Bruxelles] Demaison, Jean [Université de Lille I] Fayt, André [UCL] Puzzarini, C. [Università degli Studi di Bologna] Herman, Michel [Université Libre de Bruxelles]

The equilibrium structure of acetylene (also named ethyne) has been reinvestigated to resolve the small discrepancies noted between different determinations. The size of the system as well as the large amount of available experimental data provides the quite unique opportunity to check the magnitude and relevance of various contributions to equilibrium structure as well as to verify the accuracy of experimental results. With respect to pure theoretical investigation, quantum-chemical calculations at the coupled-cluster level have been employed together with extrapolation to the basis set limit, consideration of higher excitations in the cluster operator, inclusion of core correlation effects as well as relativistic and diagonal Born–Oppenheimer corrections. In particular, it is found that the extrapolation to the complete basis set limit, the inclusion of higher excitations in the electronic-correlation treatment and the relativistic corrections are of the same order of magnitude. It also appears that a basis set as large as a core–valence quintuple-zeta set is required for accurately accounting for the inner-shell correlation contribution. From a pure experimental point of view, the equilibrium structure has been determined using very accurate rotational constants recently obtained by a “global analysis” (that is to say that all non-negligible interactions are explicitely included in the Hamiltonian matrix) of rovibrational spectra. Finally, a semi-experimental equilibrium structure (where the equilibrium rotational constants are obtained from the experimental ground state rotational constants and computed rovibrational corrections) has been obtained from the available experimental ground-state rotational constants for ten isotopic species corrected for computed vibrational corrections. Such a determination led to the revision of the ground-state rotational constants of two isotopologues, thus showing that structural determination is a good method to identify errors in experimental rotational constants. The three structures are found in a very good agreement, and our recommended values are rCC = 120.2958(7) pm and rCH = 106.164(1) pm.

Document type Article de périodique (Journal article) – Article de recherche
Publication date 2011
Language Anglais
Journal information "Journal of Chemical Physics" - Vol. 134, no. 6, p. 064119 (2011)
Peer reviewed yes
Publisher American Institute of Physics ((United States) [New York, etc.])
issn 0021-9606
e-issn 1089-7690
Publication status Publié
Affiliations Université Libre de Bruxelles - Service Chimie Quantique et Photophysique
Université de Lille I - Laboratoire de Physique des Lasers
Atomes et Molécules
UCL - SST/IMCN/NAPS - Nanoscopic Physics
Università degli Studi di Bologna - Dipartimento di Chimica “G. Ciamician
”
Keywords CISM
Links
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Bibliographic reference Liévin, J. ; Demaison, Jean ; Fayt, André ; Puzzarini, C. ; Herman, Michel. Comparison of the experimental, semi-experimental and ab initio equilibrium structures of acetylene: influence of relativistic effects and of the diagonal Born-Oppenheimer corrections.. In: Journal of Chemical Physics, Vol. 134, no. 6, p. 064119 (2011)
Permanent URL http://hdl.handle.net/2078.1/93892