Crossed-beam study of the reactions of H+2 with D2 and D+2 with H2

Krenos, John; Lehmann, Kevin K.; Tully, John C.; Hierl, Peter M.; Smith, Gregory P.

doi:10.1016/0301-0104(76)89028-3

Cited by 49 publications

(15 citation statements)

References 31 publications

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“…In this reaction there is a curve crossing in the entrance channel very close to the zero-point energy (ZPE) of the reactants, and here we shall analyze the effect of non-adiabatic transitions as a function of translational energy and vibrational excitation of the H2+ reactants. The results are compared with the available experimental data[30, 32–35] and with the previous surface hopping results[30, 36, 37]. These last results were obtained with DIM PESs[38], which do not include long-range interaction terms and are not accurate to describe H3+ fragments.…”

Section: Introductionmentioning

confidence: 85%

“…(2) using the classical molecular dynamics with quantum transitions (MDQT) of Tully[29]. The MDQT is a variant of the commonly known surface hopping applied to study the non-adiabatic reactive H + + H 2 collisions by Krenos et al [30] and supported by the experiments of Ochs and Teloy[31]. In this reaction there is a curve crossing in the entrance channel very close to the zero-point energy (ZPE) of the reactants, and here we shall analyze the effect of non-adiabatic transitions as a function of translational energy and vibrational excitation of the H2+ reactants.…”

Section: Introductionmentioning

confidence: 99%

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Non-adiabatic couplings and dynamics in proton transfer reactions of Hn+ systems: Application to H2+H2+→H+H3+ collisions

Sanz-Sanz

Aguado

Roncero

et al. 2015

The Journal of Chemical Physics

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Analytical derivatives and non-adiabatic coupling matrix elements are derived for H + n systems (n = 3-5). The method uses a generalized Hellmann-Feynman theorem applied to a multi-state description based on diatomics-in-molecules (for H + 3 ) or triatomics-in-molecules (for H + 4 and H + 5 ) formalisms, corrected with a permutationally invariant many-body term to get high accuracy. The analytical non-adiabatic coupling matrix elements are compared with ab initio calculations performed at multi-reference configuration interaction level. These magnitudes are used to calculate H 2 (v ′ = 0, j ′ = 0) + H + 2 (v, j = 0) collisions, to determine the effect of electronic transitions using a molecular dynamics method with electronic transitions. Cross sections for several initial vibrational states of H + 2 are calculated and compared with the available experimental data, yielding an excellent agreement. The effect of vibrational excitation of H + 2 reactant and its relation with non-adiabatic processes are discussed. Also, the behavior at low collisional energies, in the 1 meV-0.1 eV interval, of interest in astrophysical environments, is discussed in terms of the long range behaviour of the interaction potential which is properly described within the triatomics-in-molecules formalism. C 2015 AIP Publishing LLC. [http://dx

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Section: Introductionmentioning

confidence: 85%

Section: Introductionmentioning

confidence: 99%

Non-adiabatic couplings and dynamics in proton transfer reactions of Hn+ systems: Application to H2+H2+→H+H3+ collisions

Sanz-Sanz

Aguado

Roncero

et al. 2015

The Journal of Chemical Physics

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“…They have also developed a similar surface that allows for p orbitals (the DIM-3C surface), but this surface and other "complete" DIM surfaces (Stine and Muckerman, 1976) are more complicated functions in which matrices larger than 2 X 2 must be diagonalized for every surface evaluation. DIM has also been used to develop surfaces for reactions involving four or more atoms (Eaker and Parr, 1976), with the most extensive applications being to the H2++H2 reaction (Pederson and Porter, 1967;Krenos et al , 1976;Polak, 1976;Stine and Muckerman, 1978). The H4+ surface requires the diagonalization of an 8 X 8 matrix at every geometry, which makes dynamics studies using trajectories quite tedious, though still feasible.…”

Section: B Semiempirical and Related Methodsmentioning

confidence: 98%

The analytical representation of electronic potential-energy surfaces

1989

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This article reviews the commonly used methods for representing electronic potential-energy surfaces for small molecules and simple chemical reactions in terms of globally defined analytical functions. Four classes of methods are discussed: spline fitting methods, semiempirical methods, many-body expansion methods, and methods that represent global surfaces based on information determined along reaction paths. The application of these methods is examined in detail for four triatomic systems and one fouratom system: 0( P)+H2, Cl+HCl, H+CO, 0('D)+H2 H20~0H+H, and H+C02 OH+CO.These examples illustrate both the art and the pitfalls of representing surfaces. In addition, the consequences of different potential surface representations for the dynamics of collisions on these surfaces are discussed at length.

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“…This assumption is not valid if, for example, we regard (3) as a proton hop reaction from H þ 2 to H 2 . Experiments using deuterated species, however, have demonstrated that the four nuclei are completely scrambled [18,19].…”

Section: Production Ofmentioning

confidence: 95%