Abstract
We have constructed the 1 2A', 2 2A' and 1 2A'' potential energy surfaces for the Cl(2p) + HCl → ClH + Cl(2P) reaction, together with the non-adiabatic coupling surface between the 1 2A' and 2 2A' states. All our calculations used the MOLPRO quantum chemistry package, with Dunning's correlation consistent augmented valence triple zeta 1-electron basis set. The 1 2A' and 1 2A'' energies are calculated at the restricted open shell coupled cluster singles doubles with perturbative triples (RCCSD-T) level, whilst the 2 2A'-1 2A' 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 2A'' |L̄(x)| 1 2A') and (1 2A'' |L̄(x)| 2 2A'>. The surfaces in adiabatic 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 ab initio surfaces to produce a set of global potential energy surfaces. Convergence tests show that the height of the barrier at C2(v) geometries is 0.4361 eV for the 1 2B1 state, and occurs at a ClHCl bond angle of 137°. The collinear barrier heights are 0.4939 eV on the 2Σ(u)+ surface and 0.9416 eV on the 2Π(g) surface.
| Original language | English |
|---|---|
| Pages (from-to) | 957-966 |
| Number of pages | 10 |
| Journal | Physical Chemistry Chemical Physics |
| Volume | 1 |
| Issue number | 6 |
| DOIs | |
| Publication status | Published - Mar 15 1999 |
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ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Atomic and Molecular Physics, and Optics
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Coupled ab initio potential energy surfaces for the reaction Cl(2P) + HCl → ClH + Cl(2P). / Dobbyn, Abigail J.; Connor, J. N L; Besley, Nicholas A.; Knowles, Peter J.; Schatz, George C.
In: Physical Chemistry Chemical Physics, Vol. 1, No. 6, 15.03.1999, p. 957-966.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Coupled ab initio potential energy surfaces for the reaction Cl(2P) + HCl → ClH + Cl(2P)
AU - Dobbyn, Abigail J.
AU - Connor, J. N L
AU - Besley, Nicholas A.
AU - Knowles, Peter J.
AU - Schatz, George C
PY - 1999/3/15
Y1 - 1999/3/15
N2 - We have constructed the 1 2A', 2 2A' and 1 2A'' potential energy surfaces for the Cl(2p) + HCl → ClH + Cl(2P) reaction, together with the non-adiabatic coupling surface between the 1 2A' and 2 2A' states. All our calculations used the MOLPRO quantum chemistry package, with Dunning's correlation consistent augmented valence triple zeta 1-electron basis set. The 1 2A' and 1 2A'' energies are calculated at the restricted open shell coupled cluster singles doubles with perturbative triples (RCCSD-T) level, whilst the 2 2A'-1 2A' 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 2A'' |L̄(x)| 1 2A') and (1 2A'' |L̄(x)| 2 2A'>. The surfaces in adiabatic 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 ab initio surfaces to produce a set of global potential energy surfaces. Convergence tests show that the height of the barrier at C2(v) geometries is 0.4361 eV for the 1 2B1 state, and occurs at a ClHCl bond angle of 137°. The collinear barrier heights are 0.4939 eV on the 2Σ(u)+ surface and 0.9416 eV on the 2Π(g) surface.
AB - We have constructed the 1 2A', 2 2A' and 1 2A'' potential energy surfaces for the Cl(2p) + HCl → ClH + Cl(2P) reaction, together with the non-adiabatic coupling surface between the 1 2A' and 2 2A' states. All our calculations used the MOLPRO quantum chemistry package, with Dunning's correlation consistent augmented valence triple zeta 1-electron basis set. The 1 2A' and 1 2A'' energies are calculated at the restricted open shell coupled cluster singles doubles with perturbative triples (RCCSD-T) level, whilst the 2 2A'-1 2A' 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 2A'' |L̄(x)| 1 2A') and (1 2A'' |L̄(x)| 2 2A'>. The surfaces in adiabatic 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 ab initio surfaces to produce a set of global potential energy surfaces. Convergence tests show that the height of the barrier at C2(v) geometries is 0.4361 eV for the 1 2B1 state, and occurs at a ClHCl bond angle of 137°. The collinear barrier heights are 0.4939 eV on the 2Σ(u)+ surface and 0.9416 eV on the 2Π(g) surface.
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U2 - 10.1039/a808183b
DO - 10.1039/a808183b
M3 - Article
AN - SCOPUS:0033559993
VL - 1
SP - 957
EP - 966
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
SN - 1463-9076
IS - 6
ER -