Spectroscopy of M+Â·Rg and transport coefficients of M+ in Rg (M = Rbâ€“Fr; Rg = Heâ€“Rn)

Holly L. Hickling; Larry A. Viehland; Dessa T . Shepherd; Pavel SoldÃ¡n; Edmond P. F. Lee; Timothy G. Wright

doi:10.1039/B405221H

Spectroscopy of M⁺·Rg and transport coefficients of M⁺ in Rg (M = Rbâ€“Fr; Rg = Heâ€“Rn)†

Holly L. Hickling,^a Larry A. Viehland,*^a Dessa T . Shepherd,^a Pavel Soldán,^b Edmond P. F. Lee*^cd and Timothy G. Wright ‡*^e

Author affiliations

* Corresponding authors

^a Division of Science, Chatham College, Pittsburgh, USA
E-mail: [email protected]

^b Department of Chemistry, University of Durham, South Road, Durham, UK

^c Department of Chemistry, University of Southampton, Highfield, Southampton, UK
E-mail: [email protected]

^d Department of Applied Biology and Chemical Technology, Hong Kong Polytechnic University, Hung Hom, Hong Kong

^e Department of Chemistry, University of Sussex, Falmer, Brighton, UK
E-mail: [email protected]
Fax: +44 1273 677196

Abstract

High-level, CCSD(T), ab initio calculations are employed to determine accurate potential energy curves for the Rb⁺Â·Rg, Cs⁺Â·Rg and Fr⁺Â·Rg species (where Rg = Heâ€“Rn). Large flexible valence basis sets are combined with effective core potentials (ECPs). The potential energy curves are used to obtain spectroscopic constants and, in addition, to calculate transport coefficients for Rb⁺, Cs⁺ and Fr⁺ moving in the respective rare gas. These transport coefficients are then statistically compared to previous data. It is concluded that the potentials are reliable. Some disagreement is found with some of the Cs⁺ transport data, which is attributed to non-equilibration in the experiments performed for heavy-M⁺/light Rg combinations. A distinct advantage of the present potentials is that they are totally ab initio, and consequently do not require experimental data to which to be fitted, as do many of the various forms of model potential available.

Article information

https://doi.org/10.1039/B405221H

Article type

Paper

Submitted

07 Apr 2004

Accepted

16 Jun 2004

First published

07 Jul 2004

Download Citation

Phys. Chem. Chem. Phys., 2004,6, 4233-4239

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