| Autor: |
J. Dobbyn, Abigail, N. L. Connor, J, A. Besley, Nicholas, J. Knowles, Peter, C. Schatz, George |
| Zdroj: |
Physical Chemistry Chemical Physics (PCCP); March 21, 1999, Vol. 1 Issue: 6 p957-966, 10p |
| Abstrakt: |
We have constructed the 12A′, 22A′ and 12A″ potential energy surfaces for the Cl(2P)+HCl→ClH+Cl(2P) reaction, together with the non-adiabatic coupling surface between the 12A′ and 22A′ states. All our calculations used the MOLPRO quantum chemistry package, with Dunning's correlation consistent augmented valence triple zeta 1-electron basis set. The 12A′ and 12A″ energies are calculated at the restricted open shell coupled cluster singles doubles with perturbative triples (RCCSD-T) level, whilst the 22A′–12A′ energy difference and the non-adiabatic coupling are calculated via the multireference configuration interaction (MRCI) technique. The non-adiabatic coupling is evaluated from transition matrix elements of the angular momentum operator, namely 〈12A″∣Lx∣12A′〉 and 〈12A″∣Lx∣22A′〉. The surfaces in a diabatic representation are fitted to rotated-Morse cubic-spline functions. The empirical long-range potentials of Dubernet and Hutson (J. Phys. Chem., 1994, 98, 5844), together with empirical short range potentials, are then combined with the fitted abinitio surfaces to produce a set of global potential energy surfaces. Convergence tests show that the height of the barrier at C2v geometries is 0.4361 eV for the 12B1 state, and occurs at a ClHCl bond angle of 137°. The collinear barrier heights are 0.4939 eV on the 2Σu+ surface and 0.9416 eV on the 2Πg surface. |
| Databáze: |
Supplemental Index |
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