Quantum scattering studies of spin-orbit effects in the Cl(2P) + HCl → ClH + Cl(2P) reaction

George C Schatz, Patrick McCabe, J. N L Connor

Research output: Contribution to journalArticle

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Abstract

We present quantum scattering calculations for the Cl + HCl → ClH + Cl reaction in which we include the three electronic states that correlate asymptotically to the ground state of Cl(2P) + HCl(X 1Σ+). The potential surfaces and couplings are taken from the recent work of Maierle et al., J. Chem. Soc., Faraday Trans., 1997, 93, 709. They are based on extensive ab initio calculations for geometries in the vicinity of the lowest energy saddle-point, and on an electrostatic expansion (plus empirical dispersion and repulsion) for long range geometries including the van der Waals wells. Spin-orbit coupling has been included using a spin-orbit coupling parameter, A, that is assumed to be independent of nuclear geometry, and Coriolis interactions are incorporated accurately. The scattering calculations use a hyperspherical coordinate coupled channel method in full dimensionality. A J-shifting approximation is employed to convert cumulative reaction probabilities for total angular momentum quantum number J = 1/2 into state selected and thermal rate coefficients. Two issues have been studied: (i) the influence of the magnitude of λ on the fine-structure resolved cumulative probabilities and rate coefficients (we consider λ values that vary from 0 to ± 100% of the true Cl value), and (ii) the transition state resonance spectrum, and its variation with λ and with other parameters in the calculations. A surprising result is the existence of a range of λ where the cumulative probability for the 2P1/2 state of Cl is larger than that for the 2P3/2 state, even though 2P1/2 is disfavoured by statistical factors and only reacts via nonadiabatic coupling. This result, which is not connected with resonance formation, may arise from coherent mixing of the Ωj = 1/2 components of the 2P3/2 and 2P1/2 states in the van der Waals regions. The 2P1/2 state dominates for values of λ between the statistical and adiabatic limits when mixing converts 2P1/2 into a state that is, for linear geometries, predominantly 2Σ1/2 near the barrier. We find two significant resonances for total energies below 0.7 eV. They are associated with two quanta of asymmetric stretch excitation of the transition state and with zero or one quanta of bend excitation. These resonances are most prominent (i.e., narrowest) in the adiabatic limit of large |λ|. For |λ| ≈ 0 the resonances are largely washed out due to strong mixing between attractive fine-structure states that support the resonances and repulsive ones that produce decay.

Original languageEnglish
Pages (from-to)139-157
Number of pages19
JournalFaraday Discussions
Volume110
Publication statusPublished - 1998

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Orbits
Scattering
orbits
scattering
Geometry
geometry
fine structure
Angular momentum
Electronic states
coefficients
saddle points
Ground state
quantum numbers
excitation
Electrostatics
angular momentum
electrostatics
expansion
ground state
energy

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Quantum scattering studies of spin-orbit effects in the Cl(2P) + HCl → ClH + Cl(2P) reaction. / Schatz, George C; McCabe, Patrick; Connor, J. N L.

In: Faraday Discussions, Vol. 110, 1998, p. 139-157.

Research output: Contribution to journalArticle

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abstract = "We present quantum scattering calculations for the Cl + HCl → ClH + Cl reaction in which we include the three electronic states that correlate asymptotically to the ground state of Cl(2P) + HCl(X 1Σ+). The potential surfaces and couplings are taken from the recent work of Maierle et al., J. Chem. Soc., Faraday Trans., 1997, 93, 709. They are based on extensive ab initio calculations for geometries in the vicinity of the lowest energy saddle-point, and on an electrostatic expansion (plus empirical dispersion and repulsion) for long range geometries including the van der Waals wells. Spin-orbit coupling has been included using a spin-orbit coupling parameter, A, that is assumed to be independent of nuclear geometry, and Coriolis interactions are incorporated accurately. The scattering calculations use a hyperspherical coordinate coupled channel method in full dimensionality. A J-shifting approximation is employed to convert cumulative reaction probabilities for total angular momentum quantum number J = 1/2 into state selected and thermal rate coefficients. Two issues have been studied: (i) the influence of the magnitude of λ on the fine-structure resolved cumulative probabilities and rate coefficients (we consider λ values that vary from 0 to ± 100{\%} of the true Cl value), and (ii) the transition state resonance spectrum, and its variation with λ and with other parameters in the calculations. A surprising result is the existence of a range of λ where the cumulative probability for the 2P1/2 state of Cl is larger than that for the 2P3/2 state, even though 2P1/2 is disfavoured by statistical factors and only reacts via nonadiabatic coupling. This result, which is not connected with resonance formation, may arise from coherent mixing of the Ωj = 1/2 components of the 2P3/2 and 2P1/2 states in the van der Waals regions. The 2P1/2 state dominates for values of λ between the statistical and adiabatic limits when mixing converts 2P1/2 into a state that is, for linear geometries, predominantly 2Σ1/2 near the barrier. We find two significant resonances for total energies below 0.7 eV. They are associated with two quanta of asymmetric stretch excitation of the transition state and with zero or one quanta of bend excitation. These resonances are most prominent (i.e., narrowest) in the adiabatic limit of large |λ|. For |λ| ≈ 0 the resonances are largely washed out due to strong mixing between attractive fine-structure states that support the resonances and repulsive ones that produce decay.",
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N2 - We present quantum scattering calculations for the Cl + HCl → ClH + Cl reaction in which we include the three electronic states that correlate asymptotically to the ground state of Cl(2P) + HCl(X 1Σ+). The potential surfaces and couplings are taken from the recent work of Maierle et al., J. Chem. Soc., Faraday Trans., 1997, 93, 709. They are based on extensive ab initio calculations for geometries in the vicinity of the lowest energy saddle-point, and on an electrostatic expansion (plus empirical dispersion and repulsion) for long range geometries including the van der Waals wells. Spin-orbit coupling has been included using a spin-orbit coupling parameter, A, that is assumed to be independent of nuclear geometry, and Coriolis interactions are incorporated accurately. The scattering calculations use a hyperspherical coordinate coupled channel method in full dimensionality. A J-shifting approximation is employed to convert cumulative reaction probabilities for total angular momentum quantum number J = 1/2 into state selected and thermal rate coefficients. Two issues have been studied: (i) the influence of the magnitude of λ on the fine-structure resolved cumulative probabilities and rate coefficients (we consider λ values that vary from 0 to ± 100% of the true Cl value), and (ii) the transition state resonance spectrum, and its variation with λ and with other parameters in the calculations. A surprising result is the existence of a range of λ where the cumulative probability for the 2P1/2 state of Cl is larger than that for the 2P3/2 state, even though 2P1/2 is disfavoured by statistical factors and only reacts via nonadiabatic coupling. This result, which is not connected with resonance formation, may arise from coherent mixing of the Ωj = 1/2 components of the 2P3/2 and 2P1/2 states in the van der Waals regions. The 2P1/2 state dominates for values of λ between the statistical and adiabatic limits when mixing converts 2P1/2 into a state that is, for linear geometries, predominantly 2Σ1/2 near the barrier. We find two significant resonances for total energies below 0.7 eV. They are associated with two quanta of asymmetric stretch excitation of the transition state and with zero or one quanta of bend excitation. These resonances are most prominent (i.e., narrowest) in the adiabatic limit of large |λ|. For |λ| ≈ 0 the resonances are largely washed out due to strong mixing between attractive fine-structure states that support the resonances and repulsive ones that produce decay.

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