Topography of potential-energy surfaces. DIM (diatomics-in-molecules) surface for Cl + Cl2
- 1 January 1984
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Journal of the Chemical Society, Faraday Transactions 2: Molecular and Chemical Physics
- Vol. 80 (7) , 809-816
- https://doi.org/10.1039/f29848000809
Abstract
Potential-energy surfaces have been calculated over the full range of nuclear configurations for the Cl + Cl2 reaction using the DIM (diatomics-in-molecules) method with the 28 poly-atomic basis functions of 2A′ symmetry and the 26 of 2A″ symmetry arising from three Cl(2Pu) atoms. The lowest 2A′ surface has its lowest potential-energy barrier Eb≈ 28 kJ mol–1 in a configuration bent by ca. 35° from the collinear configuration with 2Σ+ g symmetry. The lowest 2A″ surface has its lowest barrier Eb≈ 75 kJ mol–1 in the collinear configuration with 2Πu symmetry. Comparison with previous calculations on the F + F2 reaction shows that the barrier heights are lower and the bent configuration more energetically favoured over the collinear configuration on the 2A′ surface, in accord with Walsh molecular-orbital theory. However, the predicted increase in bending of the 2A′ transition state for Cl3 compared with F3 is observed to only a small extent (ca. 5°)Keywords
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