A new <i>ab initio</i> potential-energy surface of HO2(X2A″) and quantum studies of HO2 vibrational spectrum and rate constants for the H+O2↔O+OH reactions

Xu, Chuanxiu; Xie, Daiqian; Zhang, Dong Hui; Lin, Shi Ying; Guo, Hua

doi:10.1063/1.1944290

Cited by 112 publications

(104 citation statements)

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“…We present in Fig. 1 [57,58], referred to as the XXZLG PES. The XX-ZLG PES has been used in a number of quantum dynamics calculations of the O + OH system at high collision energies [53,54,59].…”

Section: Methodology a Potential Energy Surfacesmentioning

confidence: 99%

Formation of molecular oxygen in ultracoldO+OHcollisions

2009

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We discuss the formation of molecular oxygen in ultracold collisions between hydroxyl radicals and atomic oxygen. A time-independent quantum formalism based on hyperspherical coordinates is employed for the calculations. Elastic, inelastic and reactive cross sections as well as the vibrational and rotational populations of the product O2 molecules are reported. A J-shifting approximation is used to compute the rate coefficients. At temperatures T = 10 − 100 mK for which the OH molecules have been cooled and trapped experimentally, the elastic and reactive rate coefficients are of comparable magnitude, while at colder temperatures, T < 1 mK, the formation of molecular oxygen becomes the dominant pathway. The validity of a classical capture model to describe cold collisions of OH and O is also discussed. While very good agreement is found between classical and quantum results at T = 0.3 K, at higher temperatures, the quantum calculations predict a larger rate coefficient than the classical model, in agreement with experimental data for the O + OH reaction. The zero-temperature limiting value of the rate coefficient is predicted to be about 6 × 10 −12 cm 3 molecule −1 s −1 , a value comparable to that of barrierless alkali-metal atom -dimer systems and about a factor of five larger than that of the tunneling dominated F + H2 reaction.

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Section: Methodology a Potential Energy Surfacesmentioning

confidence: 99%

Formation of molecular oxygen in ultracoldO+OHcollisions

2009

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“…2,5,[34][35][36] The most widely used is the DMBE IV surface 34 due to Pastrana et al which was published more than 15 years ago. Troe and Ushakov designed a global surface 2 ͑designated TU͒ on the basis of Harding's ab initio calculations along the minimum energy path of the HO 2 → H+O 2 and HO 2 → HO + O dissociations.…”

Section: Introductionmentioning

confidence: 99%

State-to-state reaction probabilities for the H+O2(v,j)→O+OH(v′,j′) reaction on three potential energy surfaces

Hankel

Smith

Meijer

2007

The Journal of Chemical Physics

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A new ab initio intermolecular potential energy surface and predicted rotational spectra of the Kr−H2O complex J. Chem. Phys. 137, 224314 (2012) Our results show that the total reaction probabilities from both the TU and XXZLG surfaces are much smaller in magnitude for collision energies above 1.2 eV compared to the DMBE IV surface. The three surfaces also show different behavior with regards to the effect of initial state excitation. The reactivity is increased on the XXZLG and the TU surfaces and decreased on the DMBE IV surface. Vibrational and rotational product state distributions for the XXZLG and the DMBE IV surface show different behaviors for both types of distributions. Our results show that for energies above 1.25 eV the dynamics on the DMBE IV surface are not statistical. However, there is also evidence that the dynamics on the XXZLG surface are not purely statistical for energies above the onset of the first excited product vibrational state vЈ = 1. The magnitude of the total reaction probability is decreased for J Ͼ 0 for the DMBE IV and the XXZLG surfaces for ground-state reactants. However, for initially rovibrationally excited reactants, the total reaction probability does not decrease as expected for both surfaces. As a result the total cross section averaged over all Boltzmann accessible rotational states may well be larger than the cross section reported in the literature for j =1.

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“…20,24 Also, as in all recent investigations of the OH+ O reaction, in the scattering calculations we ignored the electronic orbital and spin angular momenta, assuming that the rotational level structure of the reactant ͑OH͒ and product ͑O 2 ͒ diatomics was that of a closed-shell molecule.…”

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confidence: 99%