Gaussian-2 and Gaussian-3 study of the energetics and structures of Cl2On and Cl2On +, n = 1-7

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journalpeer-review

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Detail(s)

Original languageEnglish
Pages (from-to)3197-3203
Journal / PublicationJournal of Physical Chemistry A
Volume104
Issue number14
Publication statusPublished - 2000
Externally publishedYes

Abstract

The structures and energetics of the dichlorine oxides, Cl2On, n = 1 -7, and their cations have been investigated theoretically at the Gaussian-2 (G2) and the Gaussian-3 (G3) levels of theory. The G2 and G3 heats of formation obtained for both neutral and cationic species allow the interpretation of assigned appearance energies and ionization energies reported in a recent photoionization mass spectrometric study (Rühl et al. Int. J. Mass Spectrom. 1999, 185, 545) on these chlorine oxides. The calculations predict that Cl2O6 + dissociates spontaneously to ClO2O+ and ClO4, in agreement with the nonobservation of Cl2O6 + in the experimental study by Rühl et al. For systems with n ≤ 4, the calculated and experimental thermochemical properties (such as heats of formation and ionization energies) are in good to excellent agreement with each other. However, this agreement deteriorates as the size of the molecular system increases or as n exceeds 4. Thus it appears that the G3 method may also suffer from "an unfavorable accumulation of component small errors," as has been found for the G2 method and its variants.

Citation Format(s)

Gaussian-2 and Gaussian-3 study of the energetics and structures of Cl2On and Cl2On +, n = 1-7. / Li, Wai-Kee; Lau, Kai-Chung; Ng, C. Y. et al.

In: Journal of Physical Chemistry A, Vol. 104, No. 14, 2000, p. 3197-3203.

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journalpeer-review