Influence of spin-orbit effects on chemical reactions

Quantum scattering studies for the Cl(2P) + HCl → ClH + Cl(2P) reactions using coupled ab initio potential energy surfaces

George C Schatz, Marlies Hankel, T. W J Whiteley, J. N L Connor

Research output: Contribution to journalArticle

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Abstract

We present converged quantum scattering results for the Cl + HCl → ClH + Cl reaction in which the three electronic states that correlate asymptotically to the ground state of Cl(2P) + HCl(1Σ+) are included in the dynamical calculations. The potential energy surfaces are taken from recent restricted open-shell coupled-cluster singles doubles with perturbative triples and multireference configuration interaction ab initio computations of A. J. Dobbyn, J. N. L. Connor, N. A. Besley, P. J. Knowles, and G. C. Schatz [Phys. Chem. Chem. Phys. 1999, 1, 957], as refined by T. W. J. Whiteley, A. J. Dobbyn, J. N. L. Connor, and G. C. Schatz [Phys. Chem. Chem. Phys. 2000, 2, 549]. The long-range van der Waals portions of the potential surfaces are derived from multisurface empirical potentials due to M.-L. Dubernet and J. M. Hutson [J. Phys. Chem. 1994, 98, 5844]. Spin-orbit coupling has been included using a spin-orbit parameter that is assumed to be independent of nuclear geometry, and Coriolis interations are calculated accurately. Reactive scattering calculations have been performed for total angular momentum quantum number J = 1/2 using a hyperspherical-coordinate coupled-channel method in full dimensionality. The scattering calculations are used to study the influence of the spin-orbit coupling parameter λ on the fine-structure-resolved cumulative reaction probabilities and transition-state resonance energies with λ varying from -150% to +150% of the true Cl value. The results show the expected dominance of the 2P3/2 state to overall reactivity for λ close to the true Cl value and the dominance of the 2P1/2 state for λ close to -1 times the true Cl value. Between these two limits, the fine-structure-resolved cumulative reaction probabilities show oscillations as λ varies, statistical behavior being recovered for λ = 0. We present a two-state model that roughly matches these oscillations and which suggests that the reactivity oscillations are due to coherent mixing of the Ωj = 1/2 components of the 2Σ and 2Π states that are derived from the 2P states in the van der Waals regions of the potential surfaces. This mixing leads to inverted spin-orbit propensities (i.e., the upper spin-orbit state is more reactive than the lower one) for certain values of λ. Our analysis of resonance energies indicates significant variation in resonance stability with the value of λ, a general trend being that narrower resonances occur when |λ| is smaller than about 50% of the absolute value of the true Cl value, suggesting that narrow resonances occur when there is significant coherent mixing. In addition, we find evidence for Stueckelberg interference oscillations in the total cumulative reaction probabilities due to a conical intersection between the 1 2A′ and 2 2A′ potential surfaces.

Original languageEnglish
Pages (from-to)7278-7289
Number of pages12
JournalJournal of Physical Chemistry A
Volume107
Issue number37
DOIs
Publication statusPublished - Sep 18 2003

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Potential energy surfaces
Chemical reactions
chemical reactions
Orbits
potential energy
Scattering
orbits
scattering
oscillations
reactivity
fine structure
Angular momentum
Electronic states
intersections
Ground state
configuration interaction
quantum numbers
angular momentum
trends
interference

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Influence of spin-orbit effects on chemical reactions : Quantum scattering studies for the Cl(2P) + HCl → ClH + Cl(2P) reactions using coupled ab initio potential energy surfaces. / Schatz, George C; Hankel, Marlies; Whiteley, T. W J; Connor, J. N L.

In: Journal of Physical Chemistry A, Vol. 107, No. 37, 18.09.2003, p. 7278-7289.

Research output: Contribution to journalArticle

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title = "Influence of spin-orbit effects on chemical reactions: Quantum scattering studies for the Cl(2P) + HCl → ClH + Cl(2P) reactions using coupled ab initio potential energy surfaces",
abstract = "We present converged quantum scattering results for the Cl + HCl → ClH + Cl reaction in which the three electronic states that correlate asymptotically to the ground state of Cl(2P) + HCl(1Σ+) are included in the dynamical calculations. The potential energy surfaces are taken from recent restricted open-shell coupled-cluster singles doubles with perturbative triples and multireference configuration interaction ab initio computations of A. J. Dobbyn, J. N. L. Connor, N. A. Besley, P. J. Knowles, and G. C. Schatz [Phys. Chem. Chem. Phys. 1999, 1, 957], as refined by T. W. J. Whiteley, A. J. Dobbyn, J. N. L. Connor, and G. C. Schatz [Phys. Chem. Chem. Phys. 2000, 2, 549]. The long-range van der Waals portions of the potential surfaces are derived from multisurface empirical potentials due to M.-L. Dubernet and J. M. Hutson [J. Phys. Chem. 1994, 98, 5844]. Spin-orbit coupling has been included using a spin-orbit parameter that is assumed to be independent of nuclear geometry, and Coriolis interations are calculated accurately. Reactive scattering calculations have been performed for total angular momentum quantum number J = 1/2 using a hyperspherical-coordinate coupled-channel method in full dimensionality. The scattering calculations are used to study the influence of the spin-orbit coupling parameter λ on the fine-structure-resolved cumulative reaction probabilities and transition-state resonance energies with λ varying from -150{\%} to +150{\%} of the true Cl value. The results show the expected dominance of the 2P3/2 state to overall reactivity for λ close to the true Cl value and the dominance of the 2P1/2 state for λ close to -1 times the true Cl value. Between these two limits, the fine-structure-resolved cumulative reaction probabilities show oscillations as λ varies, statistical behavior being recovered for λ = 0. We present a two-state model that roughly matches these oscillations and which suggests that the reactivity oscillations are due to coherent mixing of the Ωj = 1/2 components of the 2Σ and 2Π states that are derived from the 2P states in the van der Waals regions of the potential surfaces. This mixing leads to inverted spin-orbit propensities (i.e., the upper spin-orbit state is more reactive than the lower one) for certain values of λ. Our analysis of resonance energies indicates significant variation in resonance stability with the value of λ, a general trend being that narrower resonances occur when |λ| is smaller than about 50{\%} of the absolute value of the true Cl value, suggesting that narrow resonances occur when there is significant coherent mixing. In addition, we find evidence for Stueckelberg interference oscillations in the total cumulative reaction probabilities due to a conical intersection between the 1 2A′ and 2 2A′ potential surfaces.",
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T2 - Quantum scattering studies for the Cl(2P) + HCl → ClH + Cl(2P) reactions using coupled ab initio potential energy surfaces

AU - Schatz, George C

AU - Hankel, Marlies

AU - Whiteley, T. W J

AU - Connor, J. N L

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N2 - We present converged quantum scattering results for the Cl + HCl → ClH + Cl reaction in which the three electronic states that correlate asymptotically to the ground state of Cl(2P) + HCl(1Σ+) are included in the dynamical calculations. The potential energy surfaces are taken from recent restricted open-shell coupled-cluster singles doubles with perturbative triples and multireference configuration interaction ab initio computations of A. J. Dobbyn, J. N. L. Connor, N. A. Besley, P. J. Knowles, and G. C. Schatz [Phys. Chem. Chem. Phys. 1999, 1, 957], as refined by T. W. J. Whiteley, A. J. Dobbyn, J. N. L. Connor, and G. C. Schatz [Phys. Chem. Chem. Phys. 2000, 2, 549]. The long-range van der Waals portions of the potential surfaces are derived from multisurface empirical potentials due to M.-L. Dubernet and J. M. Hutson [J. Phys. Chem. 1994, 98, 5844]. Spin-orbit coupling has been included using a spin-orbit parameter that is assumed to be independent of nuclear geometry, and Coriolis interations are calculated accurately. Reactive scattering calculations have been performed for total angular momentum quantum number J = 1/2 using a hyperspherical-coordinate coupled-channel method in full dimensionality. The scattering calculations are used to study the influence of the spin-orbit coupling parameter λ on the fine-structure-resolved cumulative reaction probabilities and transition-state resonance energies with λ varying from -150% to +150% of the true Cl value. The results show the expected dominance of the 2P3/2 state to overall reactivity for λ close to the true Cl value and the dominance of the 2P1/2 state for λ close to -1 times the true Cl value. Between these two limits, the fine-structure-resolved cumulative reaction probabilities show oscillations as λ varies, statistical behavior being recovered for λ = 0. We present a two-state model that roughly matches these oscillations and which suggests that the reactivity oscillations are due to coherent mixing of the Ωj = 1/2 components of the 2Σ and 2Π states that are derived from the 2P states in the van der Waals regions of the potential surfaces. This mixing leads to inverted spin-orbit propensities (i.e., the upper spin-orbit state is more reactive than the lower one) for certain values of λ. Our analysis of resonance energies indicates significant variation in resonance stability with the value of λ, a general trend being that narrower resonances occur when |λ| is smaller than about 50% of the absolute value of the true Cl value, suggesting that narrow resonances occur when there is significant coherent mixing. In addition, we find evidence for Stueckelberg interference oscillations in the total cumulative reaction probabilities due to a conical intersection between the 1 2A′ and 2 2A′ potential surfaces.

AB - We present converged quantum scattering results for the Cl + HCl → ClH + Cl reaction in which the three electronic states that correlate asymptotically to the ground state of Cl(2P) + HCl(1Σ+) are included in the dynamical calculations. The potential energy surfaces are taken from recent restricted open-shell coupled-cluster singles doubles with perturbative triples and multireference configuration interaction ab initio computations of A. J. Dobbyn, J. N. L. Connor, N. A. Besley, P. J. Knowles, and G. C. Schatz [Phys. Chem. Chem. Phys. 1999, 1, 957], as refined by T. W. J. Whiteley, A. J. Dobbyn, J. N. L. Connor, and G. C. Schatz [Phys. Chem. Chem. Phys. 2000, 2, 549]. The long-range van der Waals portions of the potential surfaces are derived from multisurface empirical potentials due to M.-L. Dubernet and J. M. Hutson [J. Phys. Chem. 1994, 98, 5844]. Spin-orbit coupling has been included using a spin-orbit parameter that is assumed to be independent of nuclear geometry, and Coriolis interations are calculated accurately. Reactive scattering calculations have been performed for total angular momentum quantum number J = 1/2 using a hyperspherical-coordinate coupled-channel method in full dimensionality. The scattering calculations are used to study the influence of the spin-orbit coupling parameter λ on the fine-structure-resolved cumulative reaction probabilities and transition-state resonance energies with λ varying from -150% to +150% of the true Cl value. The results show the expected dominance of the 2P3/2 state to overall reactivity for λ close to the true Cl value and the dominance of the 2P1/2 state for λ close to -1 times the true Cl value. Between these two limits, the fine-structure-resolved cumulative reaction probabilities show oscillations as λ varies, statistical behavior being recovered for λ = 0. We present a two-state model that roughly matches these oscillations and which suggests that the reactivity oscillations are due to coherent mixing of the Ωj = 1/2 components of the 2Σ and 2Π states that are derived from the 2P states in the van der Waals regions of the potential surfaces. This mixing leads to inverted spin-orbit propensities (i.e., the upper spin-orbit state is more reactive than the lower one) for certain values of λ. Our analysis of resonance energies indicates significant variation in resonance stability with the value of λ, a general trend being that narrower resonances occur when |λ| is smaller than about 50% of the absolute value of the true Cl value, suggesting that narrow resonances occur when there is significant coherent mixing. In addition, we find evidence for Stueckelberg interference oscillations in the total cumulative reaction probabilities due to a conical intersection between the 1 2A′ and 2 2A′ potential surfaces.

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