Coupled ab initio potential energy surfaces for the reaction Cl(2P) + HCl → ClH + Cl(2P)

Abigail J. Dobbyn, J. N L Connor, Nicholas A. Besley, Peter J. Knowles, George C Schatz

Research output: Contribution to journalArticle

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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 languageEnglish
Pages (from-to)957-966
Number of pages10
JournalPhysical Chemistry Chemical Physics
Volume1
Issue number6
DOIs
Publication statusPublished - Mar 15 1999

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Potential energy surfaces
potential energy
Quantum chemistry
Angular momentum
spline functions
Splines
quantum chemistry
configuration interaction
Geometry
Electrons
angular momentum
valence
operators
energy
geometry

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 journalArticle

Dobbyn, Abigail J. ; Connor, J. N L ; Besley, Nicholas A. ; Knowles, Peter J. ; Schatz, George C. / Coupled ab initio potential energy surfaces for the reaction Cl(2P) + HCl → ClH + Cl(2P). In: Physical Chemistry Chemical Physics. 1999 ; Vol. 1, No. 6. pp. 957-966.
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