The Extent of Non–Born-Oppenheimer Coupling in the Reaction of Cl(
 2
 P
 ) with
 para-
 H
 2

Wang, Xingan; Dong, Wenrui; Xiao, Chunlei; Che, Li; Ren, Zefeng; Dai, Dongxu; Wang, Xiuyan; Casavecchia, Piergiorgio; Yang, Xueming; Jiang, Bin; Xie, Daiqian; Lee, Soo‐Y.; Zhang, Dong H.; Werner, Hans‐Joachim; Alexander, Millard H.

doi:10.1126/science.1163195

Cited by 98 publications

(59 citation statements)

References 29 publications

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“…Recent progress in quantum scattering has demonstrated its prowess in accurately predicting and interpreting reaction dynamics from first principles in small molecular systems, particularly for direct hydrogen abstraction (X þ H 2 → XH þ H, X ¼ H; F; Cl) reactions (23)(24)(25)(26). Such achievements relied on accurate determination of potential energy surfaces (PESs) and efficient methods for solving the nuclear Schrödinger equation (27).…”

Section: Resultsmentioning

confidence: 99%

State-to-state quantum dynamics of O + O ₂ isotope exchange reactions reveals nonstatistical behavior at atmospheric conditions

Sun

Liu

Lin

et al. 2009

Proc. Natl. Acad. Sci. U.S.A.

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The O þ O 2 exchange reaction is a prerequisite for the formation of ozone in Earth's atmosphere. We report here state-to-state differential and integral cross sections for several O þ O 2 isotopeexchange reactions obtained by dynamically exact quantum scattering calculations at collision energies relevant to atmospheric conditions. These reactions are shown to be highly nonstatistical, evidenced by dominant forward scattering and deviation of the integral cross section from the statistical limit. Mechanistic analyses revealed that the nonstatistical channel is facilitated by shortlived osculating resonances. The theoretical results provided an in-depth interpretation of a recent molecular beam experiment of the exchange reaction and shed light on the initial step of ozone recombination.complex-forming reactions | isotope effects | ozone | reactive scattering M ost chemical reactions need be activated to overcome the energy barrier, but many others require little or no activation because the intrinsic reaction path is barrierless (1). The latter type of reactions typically involves free radicals. Even at very low energies, their encounters lead to a relatively stable intermediate complex, which eventually breaks up to form products. Such complex-forming reactions are prevalent in interstellar clouds, in atmospheres, and in other gas-phase conditions such as combustion. The complex-forming mechanism manifests in various measurable attributes, such as a non-Arrhenius rate constant and a product angular distribution peaked in both forward and backward directions. exchange reaction is a prototypical complex-forming reaction via the metastable ozone (O Ã3 ) intermediate, supported by a ∼1.13 eV potential well (2). The importance of this reaction derives from the fact that it is a prerequisite for the formation of ozone in Earth's atmosphere (3, 4):in which the metastable ozone formed during the exchange reaction is stabilized by collisions with a third body (M). An in-depth understanding of the bimolecular isotope exchange reactions will not only advance our knowledge of complex-forming reactions in general, but also shed light on the surprising and significant enrichment of heavy ozone isotopomers discovered in the stratosphere (5) and in laboratory settings (6) more than 20 years ago. A key issue for a complex-forming reaction is whether it is statistical or not. If the reaction is dominated by a sufficiently longlived intermediate, the reactivity is completely determined by the availability of open channels at a given energy (7,8), and dynamics becomes unimportant. This simple statistical picture has been very successful in understanding many complex-forming reactions (9). On the other hand, ample examples can be found for nonstatistical complex-forming reactions (10-12), often due to the short lifetime of the so-called "osculating" intermediate complex (13).Recently, van Wyngarden et al. (11) reported an important crossed molecular beam study of the 16 O þ 36 O 2 → 34 O 2 þ 18 O exchange reaction at 0.32 eV of co...

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Section: Resultsmentioning

confidence: 99%

State-to-state quantum dynamics of O + O ₂ isotope exchange reactions reveals nonstatistical behavior at atmospheric conditions

Sun

Liu

Lin

et al. 2009

Proc. Natl. Acad. Sci. U.S.A.

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“…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

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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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“…Our group has been studying the details of the infrared-induced chemical reaction, Cl( 2 P 3/2 ) + H 2 (v = 1) → HCl + H, in highly enriched (99.99%) parahydrogen (pH 2 ) crystals at temperatures around 2 K [2][3][4][5]. This prototypical hydrogen abstraction reaction proceeds at these low temperatures via vibrational excitation of the H 2 reagent since the reaction of Cl with H 2 (v = 0) has a ~1900 cm -1 barrier and is + 360 cm -1 endothermic [6][7][8]. To better understand the photochemical mechanism by which infrared (IR) light creates H 2 (v = 1) and triggers the Cl + H 2 reaction, we studied the IR-induced reaction kinetics as a function of the orthohydrogen (oH 2 ) concentration in the solid.…”

Section: Introductionmentioning

confidence: 99%

Infrared studies of ortho-para conversion at Cl-atom and H-atom impurity centers in cryogenic solid hydrogen

Kettwich

Anderson

2010

Low Temperature Physics

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We report infrared spectroscopic studies of H 2 ortho-para (o/p) conversion in solid hydrogen doped with Clatoms at 2 K while the Cl + H 2 (v = 1) → HCl + H infrared-induced chemical reaction is occurring. The Cl-atom doped hydrogen crystals are synthesized using 355 nm in situ photodissociation of Cl 2 precursor molecules. For hydrogen solids with high ortho-H 2 fractional concentrations (X o = 0.55), the o/p conversion kinetics is dominated by Cl-atom catalyzed conversion with a catalyzed conversion rate constant K cc = 1.16 (11)

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The Extent of Non–Born-Oppenheimer Coupling in the Reaction of Cl( ² P ) with para- H ₂

Cited by 98 publications

References 29 publications

State-to-state quantum dynamics of O + O ₂ isotope exchange reactions reveals nonstatistical behavior at atmospheric conditions

State-to-state quantum dynamics of O + O ₂ isotope exchange reactions reveals nonstatistical behavior at atmospheric conditions

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

Infrared studies of ortho-para conversion at Cl-atom and H-atom impurity centers in cryogenic solid hydrogen

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The Extent of Non–Born-Oppenheimer Coupling in the Reaction of Cl( 2 P ) with para- H 2

Cited by 98 publications

References 29 publications

State-to-state quantum dynamics of O + O 2 isotope exchange reactions reveals nonstatistical behavior at atmospheric conditions

State-to-state quantum dynamics of O + O 2 isotope exchange reactions reveals nonstatistical behavior at atmospheric conditions

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

Infrared studies of ortho-para conversion at Cl-atom and H-atom impurity centers in cryogenic solid hydrogen

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The Extent of Non–Born-Oppenheimer Coupling in the Reaction of Cl( ² P ) with para- H ₂

State-to-state quantum dynamics of O + O ₂ isotope exchange reactions reveals nonstatistical behavior at atmospheric conditions

State-to-state quantum dynamics of O + O ₂ isotope exchange reactions reveals nonstatistical behavior at atmospheric conditions