The effect of spin–orbit coupling on the thermal rate constant of the H<sub>2</sub>+ Cl → H + HCl reaction

Manthe, Uwe; Capecchi, Gabriella; Werner, Hans‐Joachim

doi:10.1039/b409587a

Cited by 48 publications

(62 citation statements)

References 45 publications

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“…We have also included the reaction of Cl with H 2 to form HCl and H, which is slightly endothermic (by ∼0.05 eV), along with its reverse reaction. This reaction, which is not included in the UDFA compilation, has been the subject of intensive investigation, both experimental (e.g., Kumaran et al 1994; hereafter KLM94) and theoretical (e.g., Manthe et al 2004). Here we adopted the rate coefficients recommended by KLM94 (their Equations (10), (11), and (6)), which were obtained by a fit to their own measurements together with those obtained in previous studies.…”

Section: Chemical Network For Chlorine-bearing Speciesmentioning

confidence: 99%

The Chemistry of Interstellar Molecules Containing the Halogen Elements

Neufeld

Wolfire

2009

ApJ

160

223

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Although they are only minor constituents of the interstellar medium, halogen-containing molecules are of special interest because of their unique thermochemistry. Here, we present a theoretical study of the chemistry of interstellar molecules containing the halogen elements chlorine and fluorine. We have modeled both diffuse and dense molecular clouds, making use of updated estimates for the rates of several key chemical processes. We present predictions for the abundances of the three halogen molecules that have been detected to date in the interstellar medium: HF, CF + , and HCl. As in our previous study of fluorine-bearing interstellar molecules, we predict HF to be the dominant gas-phase reservoir of fluorine within both diffuse and dense molecular clouds; we expect the Herschel Space Observatory to detect widespread absorption in the HF J = 1 − 0 transition. Our updated model now overpredicts the CF + abundance by a factor 10 relative to observations of the Orion Bar; this discrepancy has widened because we now adopt a laboratory measurement of the CF + dissociative recombination rate that is smaller than the estimate we adopted previously. This disagreement suggests that the reaction of C + with HF proceeds more slowly than the capture rate assumed in our model; a laboratory measurement of this reaction rate would be very desirable. Our model predicts diffuse cloud HCl abundances that are similar to those predicted previously and detected tentatively toward ζ Oph. Two additional species are potentially detectable from photodissociation regions: the H 2 Cl + , and HCl + molecular ions. Ortho-H 2 Cl + has its lowest-lying transition in the millimeter spectral region observable from the ground, and the lowest rotational transition of HCl + is observable with Herschel's HIFI instrument.

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Section: Chemical Network For Chlorine-bearing Speciesmentioning

confidence: 99%

The Chemistry of Interstellar Molecules Containing the Halogen Elements

Neufeld

Wolfire

2009

ApJ

160

223

View full text Add to dashboard Cite

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“…An extensive body of work, both theoretical [63][64][65][66][67][68] and experimental, 69-74 also exists for the Cl+ H 2 system and its isotopic variations. This system has played a central role in chemical kinetics and has served as a test case for bimolecular reaction rate theory.…”

Section: B Advantages Of L-shaped Grid: Cl+ H 2 Reactionmentioning

confidence: 99%

“…68͒ reported in 2000 yielded quantum thermal rate constants which agree perfectly with experiment over a wide range of temperatures. 77,66 However, the recent focus has been on the disagreement between theory and experiment for the Cl͑ 2 P 1 2 / 3 2 ͒ +H 2 reaction including spin-orbit effects. 64,72,[78][79][80][81] In the following numerical calculations, the benchmark BW PES 68 is used.…”

Section: B Advantages Of L-shaped Grid: Cl+ H 2 Reactionmentioning

confidence: 99%

Extraction of state-to-state reactive scattering attributes from wave packet in reactant Jacobi coordinates

Sun

Guo

Zhang

2010

The Journal of Chemical Physics

138

126

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The S-matrix for a scattering system provides the most detailed information about the dynamics. In this work, we discuss the calculation of S-matrix elements for the A + BC→ AB+ C, AC+ B type reaction. Two methods for extracting S-matrix elements from a single wave packet in reactant Jacobi coordinates are reviewed and compared. Both methods are capable of extracting the state-to-state attributes for both product channels from a single wave packet propagation. It is shown through the examples of H + HD, Cl+ H 2 , and H + HCl reactions that such reactant coordinate based methods are easy to implement, numerically efficient, and accurate. Additional efficiency can be gained by the use of a L-shaped grid with two-dimensional fast Fourier transform.

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“…Later reaction rate calculations for the four atom reactions [49,66], and HCl + OH → Cl + H 2 O [67] followed. Some of these studies [48,54,55,60,61,65,67] employed the MCTDH approach [8,9] to efficiently perform the real and imaginary time wave packet propagations required in these calculations.…”

Section: From Triatomics To Polyatomic Reactionsmentioning

confidence: 99%

“…In these studies, first different triatomic reactions as H 2 + Cl → H +HCl [59][60][61] and O( 3 P )+HCl → OH +Cl [45,47,54,55,62] were investigated. Here also contributions for total angular momentum J > 0 were considered and the coupling of internal motion and overall rotation were studied.…”

Section: From Triatomics To Polyatomic Reactionsmentioning

confidence: 99%

The effect of spin–orbit coupling on the thermal rate constant of the H₂+ Cl → H + HCl reaction

Cited by 48 publications

References 45 publications

The Chemistry of Interstellar Molecules Containing the Halogen Elements

The Chemistry of Interstellar Molecules Containing the Halogen Elements

Extraction of state-to-state reactive scattering attributes from wave packet in reactant Jacobi coordinates

Accurate calculations of reaction rates: predictive theory based on a rigorous quantum transition state concept

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The effect of spin–orbit coupling on the thermal rate constant of the H2+ Cl → H + HCl reaction

Cited by 48 publications

References 45 publications

The Chemistry of Interstellar Molecules Containing the Halogen Elements

The Chemistry of Interstellar Molecules Containing the Halogen Elements

Extraction of state-to-state reactive scattering attributes from wave packet in reactant Jacobi coordinates

Accurate calculations of reaction rates: predictive theory based on a rigorous quantum transition state concept

Contact Info

Product

Resources

About

The effect of spin–orbit coupling on the thermal rate constant of the H₂+ Cl → H + HCl reaction