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Relaxation during internal rotation ethane and hydrogen peroxyde

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Abstract

An ab initio SCF-LCAO-MO study of the relaxation process during internal rotation has been performed for ethane and hydrogen peroxyde. A large gaussian basis set has been used, with polarization functions. The total energy has been optimized with respect to the bond lengths and bond angles. The computed barrier for the ethane molecule is 3.07 kcal/mole with the optimized geometry (experimental 2.93 kcal/mole). For hydrogen peroxyde, this yields a cis-barrier of 10.9 kcal/mole (experimental 7.0 kcal/mole) and a trans barrier of 0.6 kcal/mole (experimental 1.1 kcal/mole), with a dihedral angle equal to 123‡ (experimental 111‡–120‡). The eclipsed or cis conformations are found to have more “open” structures than the staggered or equilibrium conformations.

Résumé

Une étude des phénomènes de relaxation liés à la rotation interne a été effectuée pour l'ethane et l'eau oxygénée par la méthode ab initio SCF-LCAO-MO. Avec une base étendue de fonctions gaussiennes comprenant des fonctions de polarisation, on minimise l'énergie par rapport aux longueurs et aux angles des liaisons. La barrière calculée pour l'ethane est de 3,07 kcal/mole (valeur expérimentale 2,93 kcal/mole). Pour l'eau oxygénée, on trouve pour les barrières cis 10,9 kcal/mole, trans 0,6 kcal/mole et pour l'angle dièdre 123‡ (values expérimentales 7,0 et 1,1 kcal/mole et 111‡–120‡). Les conformations éclipsée ou cis possèdent des structures plus «ouvertes» que les conformations en étoile ou trans.

Zusammenfassung

Der Relaxationsproze\ wÄhrend der inneren Rotation wurde für Äthan und Wasserstoffperoxid mit Hilfe einer ab initio SCF-LCAO-MO-Rechnung untersucht. Dabei wurde eine gro\e Basis von Gau\funktionen mit Polarisationsfunktionen benutzt. Die Gesamtenergie wurde unter Variation der BindungslÄnge und Bindungswinkel optimiert. Die berechnete Rotationsbarriere mit der optimalen Geometrie betrÄgt 3,07 kcal/Mol für Äthan (experimentell 2,93 kcal/Mol). Für Wasserstoffperoxid ergibt sich eine cis-Barriere von 10,9 kcal/Mol (experimentell 7,0 kcal/Mol) und eine trans-Barriere von 0,6 kcal/Mol (experimentell 1,1 kcal/Mol) sowie ein Verdrillungswinkel von 123‡ (experimentell 111‡–120‡). Die verdeckten oder cis-Konformationen besitzen mehr „offene“ Strukturen als die gestaffelten oder die Gleichgewichtskonformationen.

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Authors and Affiliations

  1. Institut de Chimie, 1 rue Blaise Pascal, 67, Strasbourg, France

    A. Veillard

  2. Centre de Physique Nucléaire Théorique, Centre de Recherches Nucléaires, F-67 Strasbourg 13, B.P. 20 CR, Cronenbourg, France

    A. Veillard

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  1. A. Veillard
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Additional information

Quantum Mechanical Calculations on Barriers to Internal Rotation. Part VI. Preceding paper, Ref. [35].

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Veillard, A. Relaxation during internal rotation ethane and hydrogen peroxyde. Theoret. Chim. Acta 18, 21–33 (1970). https://doi.org/10.1007/BF00533694

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