### Abstract

We have constructed the 1 ^{2}A', 2 ^{2}A' and 1 ^{2}A'' potential energy surfaces for the Cl(^{2}p) + HCl → ClH + Cl(^{2}P) reaction, together with the non-adiabatic coupling surface between the 1 ^{2}A' and 2 ^{2}A' 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 ^{2}A' and 1 ^{2}A'' energies are calculated at the restricted open shell coupled cluster singles doubles with perturbative triples (RCCSD-T) level, whilst the 2 ^{2}A'-1 ^{2}A' 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 ^{2}A') and (1 ^{2}A'' |L̄(x)| 2 ^{2}A'>. 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 C_{2}(v) geometries is 0.4361 eV for the 1 ^{2}B_{1} state, and occurs at a ClHCl bond angle of 137°. The collinear barrier heights are 0.4939 eV on the ^{2}Σ(u)^{+} surface and 0.9416 eV on the ^{2}Π(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

### Cite this

^{2}P) + HCl → ClH + Cl(

^{2}P).

*Physical Chemistry Chemical Physics*,

*1*(6), 957-966. https://doi.org/10.1039/a808183b

**Coupled ab initio potential energy surfaces for the reaction Cl( ^{2}P) + HCl → ClH + Cl(^{2}P).** / Dobbyn, Abigail J.; Connor, J. N L; Besley, Nicholas A.; Knowles, Peter J.; Schatz, George C.

Research output: Contribution to journal › Article

^{2}P) + HCl → ClH + Cl(

^{2}P)',

*Physical Chemistry Chemical Physics*, vol. 1, no. 6, pp. 957-966. https://doi.org/10.1039/a808183b

^{2}P) + HCl → ClH + Cl(

^{2}P). Physical Chemistry Chemical Physics. 1999 Mar 15;1(6):957-966. https://doi.org/10.1039/a808183b

}

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.

UR - http://www.scopus.com/inward/record.url?scp=0033559993&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0033559993&partnerID=8YFLogxK

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 -