Role of intersystem crossing in the dynamics of the O(<sup>3</sup>P)+ICl reaction

Powell, L. J.; Wells, D. D.; Wang, J.J.; Smith, David J.; Grice, R.

doi:10.1080/00268979600100591

Cited by 4 publications

(4 citation statements)

References 15 publications

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“…However, the proportion of the total reaction cross section arising from the singlet potential energy surface compared with the triplet potential energy surface is largely independent of the alkyl group, since this is determined by the intersystem crossing probability in the entrance valley of the potential energy surface. The low fraction ∼ 1 / 5 of the total reaction cross section which is attributed to direct reaction over the triplet potential energy surface testifies to the efficiency of intersystem crossing as previously noted for the O + ICl reaction.…”

Section: Discussionsupporting

confidence: 70%

Role of Intersystem Crossing in the Dynamics of the O(³P) + (CH₃)₂CHI, (CH₃)₃CI Reactions

1996

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Reactive scattering of O( 3 P) atoms with (CH 3 ) 2 CHI and (CH 3 ) 3 CI molecules has been studied at an initial translational energy E ∼ 51 kJ mol -1 using a supersonic beam of O atoms seeded in He buffer gas from a microwave discharge source. Sharply backward peaked angular distributions of IO product scattering are observed with distinctly higher product translational energy for the backward compared with the forward and sideways scattering. Mildly forward and backward peaked angular distributions slightly favoring the backward direction are observed for HOI product scattering with the product translational energy distribution being independent of scattering angle. The component of IO scattering with low product translational energy and the HOI scattering are both attributed to intersystem crossing from the lowest triplet 3 A′′ potential energy surface to a bound OIR intermediate on the singlet 1 A′ potential energy surface. The HOI product is formed via a five-membered ring transition state where the H atom is abstracted from a terminal CH 3 group of the alkyl radical R. The fraction of singlet OIR complexes which dissociates to HOI product compared with IO product increases from ∼0.3 for R ) C 2 H 5 to ∼0.5 for R ) (CH 3 ) 2 CH and (CH 3 ) 3 C. The backward scattered IO product is attributed to direct reaction over the triplet 3 A′′ potential energy surface and contributes a fraction ∼ 1 / 5 to the total reaction cross section largely independent of the alkyl radical.Dynamics of the O( 3 P) + (CH 3 ) 2 CHI, (CH 3 ) 3 CI Reactions

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Section: Discussionsupporting

confidence: 70%

Role of Intersystem Crossing in the Dynamics of the O(³P) + (CH₃)₂CHI, (CH₃)₃CI Reactions

1996

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“…The apparatus was the same as that employed , to study the reactive scattering of O atoms with ICl and Br 2 molecules at high initial translational energies. The radio frequency discharge source employed a vapor pressure ∼9 mbar of D 2 O in a pressure ∼140 mbar of He buffer gas maintained by bubbling He gas through liquid D 2 O in a reservoir at a temperature ∼6 °C just above the freezing point.…”

Section: Methodsmentioning

confidence: 99%

Reactive Scattering of OD Radicals with ICl and Br₂ Molecules at Initial Translational Energy E ∼ 90 kJ mol^-1

et al. 1997

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Reactive scattering of OD radicals with ICl and Br2 molecules has been studied at an initial translational energy E ∼ 90 kJ mol-1 using a supersonic beam of OD radicals seeded in He buffer gas generated from a high-temperature radio frequency discharge source. The center-of-mass angular distribution of DOI scattering from OD + ICl shows sharp forward and backward peaking with the relative intensity of the backward peak being lower by a factor ∼0.6 ± 0.1. The DOBr scattering from OD + Br2 shows broader peaking in the forward direction declining to a lower intensity ∼0.8 ± 0.2 in the backward direction. In both cases the product translational energy distributions peak at low energy with a tail extending out to higher energy. Comparison with the predictions of phase space theory indicates that the OD + ICl reaction proceeds via a DOICl collision complex with a lifetime of approximately one rotational period, while the OD + Br2 reaction shows evidence for the migration of the OD radical between the Br atoms of a DOBrBr complex. The DOICl complex corresponds to a significant well of depth E 0 ∼ 80 kJ mol-1 on the potential energy surface for the OD + ICl reaction while the potential energy surface for the OD + Br2 reaction also supports a shallow minimum.

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“…The IO reactive scattering observed in these experiments shows the O + CF 3 I reaction holding a position intermediate between the O + C 2 H 5 I reaction, which has both rebound scattering over the triplet potential energy surface and long-lived complex dynamics over the singlet potential energy surface, and the O + ICl reaction, which shows only collision complex dynamics up to an initial translational energy E ∼ 100 kJ mol -1 . The potential energy profiles for bent OIR configurations in Figure show the intersection of the triplet 3 A‘‘ and singlet 1 A‘ potential energy surfaces in the entrance valley.…”

Section: Discussionmentioning

confidence: 77%

“…The apparatus was the same as that previously employed in the study of the O + ICl reaction. A high temperature radio frequency discharge source was used to produce a supersonic beam of O( 3 P) atoms seeded in He buffer gas with peak velocity ∼ 3800 m s -1 , while a high pressure microwave discharge source was used to give a peak velocity ∼ 2350 m s -1 for O atoms seeded in He buffer gas.…”

Section: Methodsmentioning

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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Role of intersystem crossing in the dynamics of the O(³P)+ICl reaction

Cited by 4 publications

References 15 publications

Role of Intersystem Crossing in the Dynamics of the O(³P) + (CH₃)₂CHI, (CH₃)₃CI Reactions

Role of Intersystem Crossing in the Dynamics of the O(³P) + (CH₃)₂CHI, (CH₃)₃CI Reactions

Reactive Scattering of OD Radicals with ICl and Br₂ Molecules at Initial Translational Energy E ∼ 90 kJ mol^-1

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

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Role of intersystem crossing in the dynamics of the O(3P)+ICl reaction

Cited by 4 publications

References 15 publications

Role of Intersystem Crossing in the Dynamics of the O(3P) + (CH3)2CHI, (CH3)3CI Reactions

Role of Intersystem Crossing in the Dynamics of the O(3P) + (CH3)2CHI, (CH3)3CI Reactions

Reactive Scattering of OD Radicals with ICl and Br2 Molecules at Initial Translational Energy E ∼ 90 kJ mol-1

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

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Role of intersystem crossing in the dynamics of the O(³P)+ICl reaction

Role of Intersystem Crossing in the Dynamics of the O(³P) + (CH₃)₂CHI, (CH₃)₃CI Reactions

Role of Intersystem Crossing in the Dynamics of the O(³P) + (CH₃)₂CHI, (CH₃)₃CI Reactions

Reactive Scattering of OD Radicals with ICl and Br₂ Molecules at Initial Translational Energy E ∼ 90 kJ mol^-1

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