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Title: Coupled ab-initio potential energy surfaces for the reaction Cl({sup 2}P) + HCl -> ClH + Cl({sup 2}P).

Abstract

We have constructed the 1{sup 2}A', 2{sup 2}A' and 1{sup 2}A' potential energy surfaces for the Cl({sup 2}P)+HClClH+Cl({sup 2}P) reaction, together with the non-adiabatic coupling surface between the 1{sup 2}A' and 2{sup 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{sup 2}A' and 1{sup 2}A' energies are calculated at the restricted open shell coupled cluster singles doubles with perturbative triples (RCCSD-T) level, whilst the 2{sup 2}A'-1{sup 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 {l_angle}1{sup 2}A'|L{sub x}|1{sup 2}A'{r_angle} and {l_angle}1{sup 2}A'|L{sub x}|2{sup 2}A'|. 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 C{sub 2v} geometries is 0.4361 eV for the 1{sup 2}B{sub 1} state, and occurs at a ClHCl bond angle ofmore » 137{sup o}. The collinear barrier heights are 0.4939 eV on the {sup 2}{Sigma}{sub u}{sup +} surface and 0.9416 eV on the {sup 2}{Pi}{sub g} surface.« less

Authors:
; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
942451
Report Number(s):
ANL/CHM/JA-31583
Journal ID: ISSN 1463-9076; TRN: US200916%%479
DOE Contract Number:  
DE-AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
Phys. Chem. Chem. Phys.
Additional Journal Information:
Journal Volume: 1; Journal Issue: 6 ; Mar. 1999; Journal ID: ISSN 1463-9076
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ANGULAR MOMENTUM OPERATORS; CONFIGURATION INTERACTION; COUPLING; POTENTIAL ENERGY; SURFACE POTENTIAL; HYDROCHLORIC ACID; PHOSPHIDES; CHLORIDES; CHEMICAL REACTION KINETICS

Citation Formats

Dobbyn, A J, Connor, J N. J., Besley, N A, Knowles, P J, Schatz, G C, and Chemistry. Coupled ab-initio potential energy surfaces for the reaction Cl({sup 2}P) + HCl -> ClH + Cl({sup 2}P).. United States: N. p., 1999. Web. doi:10.1039/a808183b.
Dobbyn, A J, Connor, J N. J., Besley, N A, Knowles, P J, Schatz, G C, & Chemistry. Coupled ab-initio potential energy surfaces for the reaction Cl({sup 2}P) + HCl -> ClH + Cl({sup 2}P).. United States. https://doi.org/10.1039/a808183b
Dobbyn, A J, Connor, J N. J., Besley, N A, Knowles, P J, Schatz, G C, and Chemistry. 1999. "Coupled ab-initio potential energy surfaces for the reaction Cl({sup 2}P) + HCl -> ClH + Cl({sup 2}P).". United States. https://doi.org/10.1039/a808183b.
@article{osti_942451,
title = {Coupled ab-initio potential energy surfaces for the reaction Cl({sup 2}P) + HCl -> ClH + Cl({sup 2}P).},
author = {Dobbyn, A J and Connor, J N. J. and Besley, N A and Knowles, P J and Schatz, G C and Chemistry},
abstractNote = {We have constructed the 1{sup 2}A', 2{sup 2}A' and 1{sup 2}A' potential energy surfaces for the Cl({sup 2}P)+HClClH+Cl({sup 2}P) reaction, together with the non-adiabatic coupling surface between the 1{sup 2}A' and 2{sup 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{sup 2}A' and 1{sup 2}A' energies are calculated at the restricted open shell coupled cluster singles doubles with perturbative triples (RCCSD-T) level, whilst the 2{sup 2}A'-1{sup 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 {l_angle}1{sup 2}A'|L{sub x}|1{sup 2}A'{r_angle} and {l_angle}1{sup 2}A'|L{sub x}|2{sup 2}A'|. 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 C{sub 2v} geometries is 0.4361 eV for the 1{sup 2}B{sub 1} state, and occurs at a ClHCl bond angle of 137{sup o}. The collinear barrier heights are 0.4939 eV on the {sup 2}{Sigma}{sub u}{sup +} surface and 0.9416 eV on the {sup 2}{Pi}{sub g} surface.},
doi = {10.1039/a808183b},
url = {https://www.osti.gov/biblio/942451}, journal = {Phys. Chem. Chem. Phys.},
issn = {1463-9076},
number = 6 ; Mar. 1999,
volume = 1,
place = {United States},
year = {1999},
month = {3}
}