Transition state dynamics of ( reactive scattering

Zhu, Z. Z.; McDouall, Joseph J. W.; Smith, David J.; Grice, R.

doi:10.1016/0009-2614(92)80859-a

Cited by 13 publications

(6 citation statements)

References 21 publications

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“…In summary, atom A first approaches atom B closely but then goes on to react with C; this is a knockout reaction. The mechanism described here is very similar to the DIPR model, − which we have shown reproduces many of the scattering features of the O + H 2 reaction . Real collisions are more complicated because the A−B−C intermediate lives long enough for it to rotate before the energy is released, so product AC molecules appear over a wide range of scattering angles.…”

Section: Resultssupporting

confidence: 62%

“…From the velocities a set of algorithms is used to select the final product state. The program uses either the sequential impulse model − or the direct interaction with product repulsion (DIPR) procedure − to treat the three-atom interaction and determine the final velocities of A, B, and C. The results of the hard sphere program are then compared with the QCT calculations; similarities and differences give insights into the reaction mechanism.…”

Section: Introductionmentioning

confidence: 99%

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Predominance of Knockout Reactions at High Energy in Collisions of X + H₂ (X = O(³P), F, Cl, T, and H)

Song

Gislason

1996

J. Phys. Chem.

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Quasiclassical trajectory studies have been carried out for the reactions of O( 3 P), F, Cl, T, and H with H 2 over a wide range of relative collision energy. For all five systems at low energy the projectile reacts only with the H atom it hits first (direct reaction), but at high energy the major product channel is the knockout reaction, where the atom hits one H atom but then goes on to react with the other one. This behavior is consistent with the direct interaction with product repulsion model and is attributed to a common feature of the potential energy surfaces, namely, a strong repulsion between the two H atoms after the system makes the rapid transition between the reactant and product regions of the surface. Evidence for the importance of knockout reactions at high energy is also seen in the angular distribution of the products, particularly in the persistence of product molecules scattered into the backward hemisphere.

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Section: Resultssupporting

confidence: 62%

Section: Introductionmentioning

confidence: 99%

Predominance of Knockout Reactions at High Energy in Collisions of X + H₂ (X = O(³P), F, Cl, T, and H)

Song

Gislason

1996

J. Phys. Chem.

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“…The backward peaking shown by the fast component of IO scattering in Figure is sharper than that predicted for hard sphere scattering even when reaction is confined to the collinear configuration. Similarly sharp backward scattering is also exhibited by the O + C 3 H 5 I reaction at higher initial translational energy E of ∼46 kJ mol -1 , where this has also been attributed to direct dynamics over the triplet potential energy surface for this more exoergic reaction.…”

Section: Discussionmentioning

confidence: 62%

“…It has been argued previously 4 that lowering of the 3 A′′ Renner Teller surface is enhanced by charge-transfer interaction of the form OI + R -. The substantial electron affinity 21 of the CF 3 radical A(CF 3 ) ∼ 172 kJ mol -1 promotes such charge transfer and lowering of the 3 A′′ potential The backward peaking shown by the fast component of IO scattering in Figure 5 is sharper than that predicted 23 for hard sphere scattering even when reaction is confined to the collinear configuration. Similarly sharp backward scattering is also exhibited by the O + C 3 H 5 I reaction at higher initial translational energy E of ∼46 kJ mol -1 , where this has also been attributed to direct dynamics over the triplet potential energy surface for this more exoergic reaction.…”

Section: CM (θU) ) I(θ)u(uθ)mentioning

confidence: 84%

Role of Renner Teller and Spin−Orbit Interaction in the Dynamics of the O(³P) + CH₂ICl Reaction

et al. 1998

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Reactive scattering of O(3P) atoms with CH2ICl molecules has been measured at initial translational energies E ∼ 46 and 17 kJ mol-1 using a supersonic beam of O atoms seeded in He and Ne buffer gases generated from a high-pressure microwave discharge source. At the higher initial translational energy, the IO product scattering can be resolved into two components; one showing forward and backward peaking with a product translational energy distribution peaking at low energy with a tail extending out to higher energy, and the other that peaks in the backward direction with higher product translational energy. At lower initial translational energy, the IO product scattering does not allow the resolution of two components but peaks in the backward direction with a higher product translational energy than for scattering in the forward hemisphere. The slow component is attributed to dissociation of a long-lived OICH2Cl complex formed by intersystem crossing from the initial triplet 3A‘‘ potential energy surface to the underlying singlet 1A‘ potential energy surface. The fast component is attributed to direct reaction over the triplet potential energy surface with the sharp backward peaking arising from reaction on the 3Π2 and 3Π1 spin multiplet surfaces in near collinear OICH2Cl configurations and the scattering in the sideways and forward directions arising from reaction on the 3A‘‘ Renner Teller surface in strongly bent configurations. The contribution of the slow component is approximately one-third that of the fast component to the total reaction cross section for IO product scattering.

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“…The approach of the O( 3 P) atom to the S atom of the thiirane molecule involves overlap of the O atom p orbital with the lone pair orbital of the S atom, corresponding to a pyramidal configuration about the S atom as shown in Figure . On the triplet 3 A‘‘ potential energy surface, repulsion will be invoked in both the C−S bonds as the π orbitals of the C 2 H 4 moiety overlap with the π orbitals of the SO moiety, leading to the formation of C 2 H 4 and SO( 3 Σ - ) reaction products.…”

Section: Discussionmentioning

confidence: 99%

Dynamics of Ring Cleavage and Substitution in the Reactive Scattering of O(³P) Atoms with C₂H₄S and C₄H₄S Molecules

et al. 1997

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Reactive scattering of ground state O( 3 P) atoms with C 2 H 4 S and C 4 H 4 S molecules has been studied at an initial translational energy E ∼ 40 kJ mol -1 using a supersonic beam of O atoms seeded in He buffer gas generated from a microwave discharge source. The center-of-mass angular distribution of SO scattering for O + C 2 H 4 S is cone-shaped in the backward hemisphere at a scattering angle θ ∼ 120°with respect to the incident O atom direction, while the OC 4 H 3 S scattering for O + C 4 H 4 S is nominally isotropic. The O + C 2 H 4 S reaction disposes a lower fraction (f ′ ∼ 0.3) of the total available energy into product translation than the O + C 4 H 4 S reaction (f ′ ∼ 0.4), although the product translational energies are higher by a factor of ∼2 for the more exoergic O + C 2 H 4 S reaction. The O + C 2 H 4 S reaction involves cleavage of the three-membered ring of the thiirane molecule, while the O + C 4 H 4 S reaction involves H atom displacement from the fivemembered ring of the thiophene molecule. Both reactions occur on the triplet potential energy surface. The strongly exoergic concerted rupture of the three-membered thiirane ring disposes half the available energy into vibrational excitation of the ethene product molecule compared with only a fraction (∼0.13) being disposed into SO product vibration. The displacement reaction of the five-membered thiophene ring involves O atom addition forming a persistent OC 4 H 4 S complex with a potential energy barrier to H atom displacement.

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Transition state dynamics of ( reactive scattering

Cited by 13 publications

References 21 publications

Predominance of Knockout Reactions at High Energy in Collisions of X + H₂ (X = O(³P), F, Cl, T, and H)

Predominance of Knockout Reactions at High Energy in Collisions of X + H₂ (X = O(³P), F, Cl, T, and H)

Role of Renner Teller and Spin−Orbit Interaction in the Dynamics of the O(³P) + CH₂ICl Reaction

Dynamics of Ring Cleavage and Substitution in the Reactive Scattering of O(³P) Atoms with C₂H₄S and C₄H₄S Molecules

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Transition state dynamics of ( reactive scattering

Cited by 13 publications

References 21 publications

Predominance of Knockout Reactions at High Energy in Collisions of X + H2 (X = O(3P), F, Cl, T, and H)

Predominance of Knockout Reactions at High Energy in Collisions of X + H2 (X = O(3P), F, Cl, T, and H)

Role of Renner Teller and Spin−Orbit Interaction in the Dynamics of the O(3P) + CH2ICl Reaction

Dynamics of Ring Cleavage and Substitution in the Reactive Scattering of O(3P) Atoms with C2H4S and C4H4S Molecules

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Predominance of Knockout Reactions at High Energy in Collisions of X + H₂ (X = O(³P), F, Cl, T, and H)

Predominance of Knockout Reactions at High Energy in Collisions of X + H₂ (X = O(³P), F, Cl, T, and H)

Role of Renner Teller and Spin−Orbit Interaction in the Dynamics of the O(³P) + CH₂ICl Reaction

Dynamics of Ring Cleavage and Substitution in the Reactive Scattering of O(³P) Atoms with C₂H₄S and C₄H₄S Molecules