Photodissociation of cyclopropyl cyanide at 193 nm

Oh, Chang‐Young; Shin, Seung Koo; Kim, Hong Lae; Park, Chan Ryang

doi:10.1016/s0009-2614(02)01242-3

Cited by 5 publications

(6 citation statements)

References 11 publications

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“…In the photodissociation of cyclopropyl iodide, where the production of allyl has been recently demonstrated, no more than 80% of the theoretical ring-opening energy appears in the translation of the products, the only degree of freedom other than the allyl rotations and vibrations. In the photodissociation of cyclopropyl cyanide, no more than 40% of this energy is available to translation and CN rotation/vibration.…”

Section: Resultsmentioning

confidence: 99%

“…Very recently, the isomeriztion of cyclopropyl to allyl has been observed in the unimolecular reaction of photoexcited cyclopropyl iodide and cyclopropyl cyanide, where the total energy far exceeds the 0.95(8)-eV barrier to ring-opening, and even here the appearance of allyl occurs only because of an unusual double curve-crossing or the production of a very highly excited intermediate. In these cases, the photofragment separation involves heavy-atom motion that is on the same time scale as the ring-opening, so the product isomerization and product separation can easily be concerted.…”

Section: Introductionmentioning

confidence: 99%

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Evidence of a Surprising Channeling of Ring-Opening Energy to the H₂ Product in the H + c-C₃H₆ → H₂ + C₃H₅ Abstraction Reaction

et al. 2003

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The product energy disposal in the abstraction reaction H + c-C3H6 → H2(v‘, j‘) + C3H5 at 1.6 eV collision energy has been characterized by quantum-state-selective, Doppler-resolved REMPI detection of the H2(v‘, j‘) product. The H2(v‘, j‘) product is observed with total energy, translational plus rotational plus vibrational, in excess of the total available energy if the C3H5 product is a cyclopropyl radical, but the total H2(v‘, j‘) energy matches the total available energy if the C3H5 product is allyl. This implies ring-opening of cyclopropyl to allyl concerted with abstraction and the deposition of a large fraction of the ring-opening energy into the H2(v‘, j‘) product. Such behavior is unprecedented and entirely unexpected. Calculations indicate that both direct H-by-H abstraction and H-addition/H2-elimination should occur too quickly to allow the isomerization to occur before product separation. Even if ring-opening did occur, the appearance of the total isomerization energy in the H2 product would seem dynamically forbidden. The reaction must follow an unanticipated and surprising path.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Evidence of a Surprising Channeling of Ring-Opening Energy to the H₂ Product in the H + c-C₃H₆ → H₂ + C₃H₅ Abstraction Reaction

et al. 2003

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“…In addition, the product of the abstraction reaction, cyclopropyl (cyc-C 3 H 5 ), can undergo a ring opening isomerization to form the thermodynamically more stable allyl radical (CH 2 CHCH 2 ) . This procedure is often used by experimentalists − to produce the allyl radical. In such experiments, cyc-C 3 H 5 are first generated by the H abstraction reaction from cyc-C 3 H 6 using a radical or atoms.…”

Section: Introductionmentioning

confidence: 99%

Quantum Dynamics of the Abstraction Reaction of H with Cyclopropane

Xiao

Clary

2014

J. Phys. Chem. A

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The dynamics of the abstraction reaction of H atoms with the cyclopropane molecule is studied using quantum mechanical scattering theory. The quantum scattering calculations are performed in hyperspherical coordinates with a two-dimensional (2D) potential energy surface. The ab initio energy calculations are carried out with CCSD(T)-F12a/cc-pVTZ-F12 level of theory with the geometry and frequency calculations at the MP2/cc-pVTZ level. The contribution to the potential energy surface from the spectator modes is included as the projected zero-point energy correction to the ab initio energy. The 2D surface is fitted with a 29-parameter double Morse potential. An R-matrix propagation scheme is carried out to solve the close-coupled equations. The adiabatic energy barrier and reaction enthalpy are compared with high level computational calculations as well as experimental data. The calculated reaction rate constants shows very good agreement when compared with the experimental data, especially at lower temperature highlighting the importance of quantum tunnelling. The reaction probabilities are also presented and discussed. The special features of performing quantum dynamics calculation on the chemical reaction of a cyclic molecule are discussed.

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“…Propargyl plays a key role in the soot formation process and particularly the initial formation of benzene . Due to these chain reactions there have been many studies on the properties and formation of allyl radicals. − Experimentists − often use the ring-opening reaction of the cyclopropyl (cyc-C 3 H 5 ) radical to produce allyl radicals. In the early experimental studies 9,10 cyclopropyl was generated by a radical- or atom-induced decomposition of cyclopropane, i.e., X + cyc-C 3 H 6 → HX + cyc-C 3 H 5 for X = CH 3 , Cl, and F, etc.…”

Section: Introductionmentioning

confidence: 99%

“…In the early experimental studies 9,10 cyclopropyl was generated by a radical- or atom-induced decomposition of cyclopropane, i.e., X + cyc-C 3 H 6 → HX + cyc-C 3 H 5 for X = CH 3 , Cl, and F, etc. Such a reaction was postulated to occur after the hydrogen-atom transfer process. − In particular, the ring-opening mechanism of the cyclopropyl radical has been studied in detail by Mann and Hase using an ab initio direct dynamics method. They found that both conrotary and disrotary ring-opening processes could happen, although they are symmetry forbidden according to the Woodward−Hoffmann rules .…”

Section: Introductionmentioning

confidence: 99%

Exploring the Multiple Reaction Pathways for the H + cyc-C₃H₆ Reaction

Muckerman

2004

J. Phys. Chem. A

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Reaction pathways for the hydrogen atom plus cyclopropane (cyc-C3H6) reaction are studied using an extrapolated coupled-cluster/complete basis set (CBS) method based on the cc-pVDZ, cc-pVTZ, and cc-pVQZ basis sets. For this activated reaction, results reveal two reaction mechanisms, a direct H-abstraction and a H-addition/ring-opening. The hydrogen-abstraction reaction yields the H2 and cyclopropyl (cyc-C3H5) radical products. The vibrationally adiabatic ground-state (VAG) barrier height is predicted to be 13.03 kcal/mol. The isomerization barrier height from the product cyclopropyl to allyl radical is 21.98 kcal/mol via a cyc-C3H5 ring-opening process. In addition, the H-addition and ring-opening mechanism will lead to an n-C3H7 radical, which can result in a variety of products such as CH3 + C2H4, H + CH3CHCH2, and H2 + C3H5, etc. The VAG barrier height of the H-addition reaction is 16.49 kcal/mol, which is slightly higher than that of the direct H-abstraction reaction. Although the H + cyc-C3H6 → CH4 + CH2CH reaction is exoergic by 11.90 kcal/mol, this reaction is unlikely due to a high barrier of 43.05 kcal/mol along the minimum energy path.

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Photodissociation of cyclopropyl cyanide at 193 nm

Cited by 5 publications

References 11 publications

Evidence of a Surprising Channeling of Ring-Opening Energy to the H₂ Product in the H + c-C₃H₆ → H₂ + C₃H₅ Abstraction Reaction

Evidence of a Surprising Channeling of Ring-Opening Energy to the H₂ Product in the H + c-C₃H₆ → H₂ + C₃H₅ Abstraction Reaction

Quantum Dynamics of the Abstraction Reaction of H with Cyclopropane

Exploring the Multiple Reaction Pathways for the H + cyc-C₃H₆ Reaction

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Photodissociation of cyclopropyl cyanide at 193 nm

Cited by 5 publications

References 11 publications

Evidence of a Surprising Channeling of Ring-Opening Energy to the H2 Product in the H + c-C3H6 → H2 + C3H5 Abstraction Reaction

Evidence of a Surprising Channeling of Ring-Opening Energy to the H2 Product in the H + c-C3H6 → H2 + C3H5 Abstraction Reaction

Quantum Dynamics of the Abstraction Reaction of H with Cyclopropane

Exploring the Multiple Reaction Pathways for the H + cyc-C3H6 Reaction

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Evidence of a Surprising Channeling of Ring-Opening Energy to the H₂ Product in the H + c-C₃H₆ → H₂ + C₃H₅ Abstraction Reaction

Evidence of a Surprising Channeling of Ring-Opening Energy to the H₂ Product in the H + c-C₃H₆ → H₂ + C₃H₅ Abstraction Reaction

Exploring the Multiple Reaction Pathways for the H + cyc-C₃H₆ Reaction