Differential cross sections for fine structure transitions in O(3<i>P</i>2)+Ar collisions

Ma, Z.; Liu, Kopin; Harding, Lawrence B.; Komotos, M.; Schatz, George C.

doi:10.1063/1.466796

Cited by 35 publications

(22 citation statements)

References 24 publications

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“…Inelastic transitions in the RgϩX( 3 P) collisions have been studied in several works, see, e.g., Refs. 29,30,[44][45][46][47]55. It is well known that the electrostatic interaction which preserves the bodyfixed projection ⍀ of j ͑and simultaneously of the total angular momentum J͒ couples the jϭ0, 2 and jϭ1, 2 pairs of levels.…”

Section: Intramultiplet Transitions In Rg¿s Collisionsmentioning

confidence: 99%

Ab initio potentials for the S(3Pj)–rare gas dimers: Implementation for elastic and inelastic collisions and comparison with scattering potentials

Kłos

Chałasiński

Krems

et al. 2002

The Journal of Chemical Physics

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Articles you may be interested inAccurate ab initio potential energy surface, thermochemistry, and dynamics of the Br(2P, 2P3/2) + CH4 → HBr + CH3 reaction J. Chem. Phys. 138, 134301 (2013); 10.1063/1.4797467Correlated ab initio investigations on the intermolecular and intramolecular potential energy surfaces in the ground electronic state of the O 2 − ( X Π g 2 ) − HF ( X Σ + 1 ) complex J. Chem. Phys. 138, 014304 (2013); 10.1063/1.4772653Ab initio potential energy surfaces, bound states, and electronic spectrum of the Ar-SH complexThe interaction potentials between the ground state S( 3 P) atom and rare gas atoms Rg ͑He, Ne, Ar, Kr, and Xe͒ in 3 ⌸ and 3 ⌺ Ϫ states are calculated ab initio using an unrestricted CCSD͑T͒ level of theory and extended correlation consistent basis sets augmented by bond functions. For NeS, the effects of extending the basis set, of a more accurate treatment of triple excitations within the coupled cluster method, and of the frozen core approximation are analyzed. The spin-orbit interaction is taken into account by the commonly used atomic model, whose validity is verified by the direct ab initio calculations of spin-orbit coupling matrix elements. The ab initio potentials are tested in the calculations of the absolute total scattering cross sections measured in molecular beams and compared with the potentials derived from the same data. This comparison, along with an analysis in terms of correlation formulas, proves the high accuracy of ab initio potentials and characterizes the sensitivity of scattering cross sections to the properties of interaction potentials. Both ab initio and scattering derived potentials are implemented in the study of inelastic fine structure transitions in SϩRg collisions. The relaxation rate constants are calculated and compared with those for OϩRg collisions.

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Section: Intramultiplet Transitions In Rg¿s Collisionsmentioning

confidence: 99%

Ab initio potentials for the S(3Pj)–rare gas dimers: Implementation for elastic and inelastic collisions and comparison with scattering potentials

Kłos

Chałasiński

Krems

et al. 2002

The Journal of Chemical Physics

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“…Using a similar setup, previous studies demonstrated that most of O atoms (∼98%) were supersonically cooled to the lowest fine-structure state O( 3 P 2 ). 29,30 Because of the high barrier to reaction, the CHD 3 beam was also seeded (∼20%) in H 2 for acceleration. To investigate the initial translational energy dependence of the reactivity, the intersection angle of the two molecular beams was varied, thereby changing the relative collision energy in the center-of-mass frame.…”

Section: Experimental Methodsmentioning

confidence: 99%

Correlated Dynamics of the O(³P) + CHD₃(v=0) Reaction: A Joint Crossed-Beam and Quasiclassical Trajectory Study

2014

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ABSTRACT:Crossed beam experiments and quasiclassical trajectory computations on an ab initio potential energy surface are performed for the O( 3 P) + CHD 3 (v=0) → OH(v′=0) + CD 3 (v 2 =0,2) and OD(v′=0,1) + CHD 2 (v=0) reactions. Both experiment and theory show that the excitation functions display a concave-up behavior and the angular distributions are backward scattered, indicating a direct rebound mechanism and a tight-bend transition state. The reaction produces mainly ground-state products showing the dominance of a vibrationally adiabatic reaction pathway. The standard histogram binning cannot reproduce the observed vibrational adiabaticity, whereas Gaussian binning gives good agreement with experiment.

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“…They have also been observed in reactive collisions of open-shell atoms with closed-shell molecules [8][9][10][11] and alignment-specific behavior in the reactive cross sections has sometimes been noted. In theoretical studies of inelastic atom-atom collisions, Coriolis effects have been addressed occasionally [12][13][14][15] but there have been essentially no theoretical studies of Coriolis effects in reactive collisions. In this paper we would like to address this issue along with other aspects of nonadiabatic reaction dynamics.…”

Section: Introductionmentioning

confidence: 99%

Quantum scattering study of electronic Coriolis and nonadiabatic coupling effects in O(1D)+H2→OH+H

Drukker

Schatz

1999

The Journal of Chemical Physics

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In this paper we develop an approximate quantum scattering method capable of determining cross sections for reactive A+BC collisions, with A being an open shell atom and BC being a closed shell diatomic molecule. This method is based on time-independent coupled channel calculations, and absorbing potentials are used to describe reaction. The coupled channel expansion includes all electronic states of the atom that correlate to a selected atomic term, and a converged set of rotational states of the diatomic. Diatomic vibration is approximated as an adiabatic degree of freedom. The method is used to study the title reaction, including all five of the electronic surfaces that correlate to O(1D)+H2 as well as terms in the Hamiltonian that couple these surfaces. These couplings include: electronic and rotational Coriolis coupling, and electrostatic nonadiabatic coupling. Coriolis coupling causes all five states to interact and is most important at long range, while electrostatic coupling produces strong interactions between the 11Σ and 11Π states at short range (where these states have a conical intersection) and weak but non-negligible interactions between these states at long range. The most important three of the five surfaces (11Σ and 11Π, or 11A′, 11A″ and 21A′) and the electrostatic nonadiabatic coupling between them are taken from the recent ab initio calculations of Dobbyn and Knowles [A. J. Dobbyn and P. J. Knowles, Mol. Phys. 91, 1107 (1997); Faraday Discuss. 110, 247 (1998)], while the other surfaces (11Δ or 21A″ and 31A′) are based on a diatomics-in-molecules potential. Our results for the fully coupled problem indicate that Coriolis coupling is significant between the electronic fine structure levels so that electronic alignment is not strongly preserved as the reactants approach. However, the fine structure averaged reaction probability is relatively insensitive to the electronic Coriolis mixing. Averaged reaction probabilities from a centrifugal decoupled calculation where both electronic and rotational Coriolis interactions are neglected are in good agreement (10% or better) with the results of the fully coupled calculations. We find that electrostatic nonadiabatic coupling between the lowest Σ and Π states is significant, even at energies below the Π barrier where only the long-range nonadiabatic coupling between these states is important. As a result, the low energy cross section summed over electronic states receives a ≈10% contribution from the Π state. We find that the total cross section decreases with energy for energies below ≈3.5 kcal/mol and increases slightly at higher energies, with the increase due to reaction over the Π barrier. We find that the Π barrier contribution to the cross section is about twice that obtained by treating the reaction adiabatically, with the difference due to nonadiabatic dynamics on the 21A′ state.

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Differential cross sections for fine structure transitions in O(3P2)+Ar collisions

Cited by 35 publications

References 24 publications

Ab initio potentials for the S(3Pj)–rare gas dimers: Implementation for elastic and inelastic collisions and comparison with scattering potentials

Ab initio potentials for the S(3Pj)–rare gas dimers: Implementation for elastic and inelastic collisions and comparison with scattering potentials

Correlated Dynamics of the O(³P) + CHD₃(v=0) Reaction: A Joint Crossed-Beam and Quasiclassical Trajectory Study

Quantum scattering study of electronic Coriolis and nonadiabatic coupling effects in O(1D)+H2→OH+H

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Differential cross sections for fine structure transitions in O(3P2)+Ar collisions

Cited by 35 publications

References 24 publications

Ab initio potentials for the S(3Pj)–rare gas dimers: Implementation for elastic and inelastic collisions and comparison with scattering potentials

Ab initio potentials for the S(3Pj)–rare gas dimers: Implementation for elastic and inelastic collisions and comparison with scattering potentials

Correlated Dynamics of the O(3P) + CHD3(v=0) Reaction: A Joint Crossed-Beam and Quasiclassical Trajectory Study

Quantum scattering study of electronic Coriolis and nonadiabatic coupling effects in O(1D)+H2→OH+H

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Correlated Dynamics of the O(³P) + CHD₃(v=0) Reaction: A Joint Crossed-Beam and Quasiclassical Trajectory Study