Reactive scattering of O(3P) atoms with alkyl and allyl iodide molecules

White, R.W.P.; Smith, David J.; Grice, R.

doi:10.1016/0009-2614(92)85666-x

Cited by 16 publications

(8 citation statements)

References 33 publications

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“…Interchange can occur between these surfaces via the avoided intersections at the crossing angle β c . When Renner Teller interaction is strong this is likely to divert trajectories from the upper 3 A‘ to the lower 3 A‘‘ potential energy surface, particularly if motion over the 3 A‘ surface is impeded by a potential energy barrier. Hence, an initial translational energy threshold for the appearance of sharply backward peaked scattering 3 may reflect a potential energy barrier on the higher 3 A‘ rather than the lower 3 A‘‘ potential energy surface.…”

Section: Discussionmentioning

confidence: 99%

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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Section: Discussionmentioning

confidence: 99%

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

et al. 1998

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“…The mild forward and backward peaking of the IO scattering from the singlet OICF 3 complex in Figure corresponds to intersystem crossing occurring in collisions at small impact parameters b < 2.5 Å with the iodine atom end of the reactant CF 3 I molecule. The mild preference for backward scattering in Figure suggests that reaction at small impact parameters may be augmented by trajectories which commence in more nearly collinear configurations on the triplet 3 A‘ potential energy surface …”

Section: Discussionmentioning

confidence: 99%

Role of Renner Teller and Spin−Orbit Interaction in the Reactive Scattering of O(³P) Atoms with CF₃I Molecules

et al. 1997

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Reactive scattering of O( 3 P) atoms with CF 3 I molecules has been studied at initial translational energies E ∼ 108 and 42 kJ mol -1 using supersonic beams of O atoms seeded in He buffer gas generated from rf and microwave discharge sources. At the higher initial translational energy, the IO scattering shows a broad peak in the forward hemisphere with respect to the initial O atom direction with a product translational energy distribution shifted to higher energy than the prediction of phase space theory. At the lower initial translational energy, the IO scattering shows a sideways peaked component with a fraction f ′ ∼ 0.4 of the total available energy being disposed into translation and a forward and backward peaked component with a product translational energy distribution in accord with the predictions of phase space theory. The sideways scattering is attributed to direct reaction over the triplet 3 A′′ potential energy surface, while the forward and backward peaked scattering is attributed to dissociation of a persistent singlet OICF 3 complex formed by intersystem crossing to the underlying 1 A′ potential energy surface. The direct scattering over the triplet 3 A′′ potential energy surface contributes a fraction, ∼0.5, to the total reaction cross section at the lower initial translational energy, while the forward scattering at the higher initial translational energy is dominated by direct reaction over the triplet 3 A′′ potential energy surface. This dynamical behavior is correlated with the effect of charge transfer interaction of the form OI + Ron Renner Teller splitting of the triplet potential energy surface.

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“…The apparatus was the same as that employed in previous preliminary experiments, except that the quadrupole mass spectrometer detector has been rebuilt to gain improved resolution of the IO + mass peak while maintaining high detection sensitivity. Supersonic beams of O( 3 P) atoms seeded in He and Ne buffer gases were produced from a high-pressure microwave discharge source .…”

Section: Methodsmentioning

confidence: 99%

“…The probability of intersystem crossing depends upon the initial translational energy, while the relative yield of HOI product depends upon the number of terminal CH 3 groups of the alkyl radical R. However, the precise location and mode of action of the seam of intersection between the triplet and singlet potential energy surfaces are not fully defined by these experimental results. In order to resolve the mechanism of intersystem crossing in the reactions of O( 3 P) atoms with hydrocarbon iodide molecules more clearly, the more exoergic reaction of allyl iodide molecules studied previously is reported in full here: …”

Section: Introductionmentioning

confidence: 99%

Role of Renner Teller and Spin−Orbit Interaction in the Dynamics of the O(³P) + C₃H₅I Reaction

1997

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Reactive scattering of O(3P) atoms with C3H5I molecules has been studied at initial translational energies E ∼ 46 and 16 kJ mol-1 using a supersonic beam of O atoms seeded in He and Ne buffer gas generated from a microwave discharge source. Strongly backward peaked angular distributions of IO product scattering are observed at both initial translational energies with the peaking becoming sharper at higher energy. The product translational energy distributions are pitched at higher energy for the backward scattering and shift progressively toward lower energy as the IO scattering moves round into the forward direction. Backward scattering with high product translational energy is attributed to direct reaction in small impact parameter collisions b ≤ 2.5 Å over the triplet potential energy surface. Scattering with low product translational energy which becomes perceptible in the forward direction is attributed to intersystem crossing to the underlying singlet potential energy surface forming a bound OIC3H5 intermediate complex. Direct reaction over the 3A‘‘ potential energy surface plays a more significant role for the exoergic allyl iodide reaction than in the nearly thermoneutral reactions of alkyl iodide molecules, where intersystem crossing to the 1A‘ potential energy surface is the predominant reaction mechanism. The dynamical basis for this difference in mechanism is discussed in terms of the topography of the potential energy surfaces involved.

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Reactive scattering of O(3P) atoms with alkyl and allyl iodide molecules

Cited by 16 publications

References 33 publications

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

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

Role of Renner Teller and Spin−Orbit Interaction in the Reactive Scattering of O(³P) Atoms with CF₃I Molecules

Role of Renner Teller and Spin−Orbit Interaction in the Dynamics of the O(³P) + C₃H₅I Reaction

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Reactive scattering of O(3P) atoms with alkyl and allyl iodide molecules

Cited by 16 publications

References 33 publications

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

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

Role of Renner Teller and Spin−Orbit Interaction in the Reactive Scattering of O(3P) Atoms with CF3I Molecules

Role of Renner Teller and Spin−Orbit Interaction in the Dynamics of the O(3P) + C3H5I Reaction

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

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

Role of Renner Teller and Spin−Orbit Interaction in the Reactive Scattering of O(³P) Atoms with CF₃I Molecules

Role of Renner Teller and Spin−Orbit Interaction in the Dynamics of the O(³P) + C₃H₅I Reaction