MINDO/3 CI Study of NCO Spectrum and the Chemiluminescent Reaction N + CO → NCO + h

Minaev, B. F.; Иванова, Н. М.; Muldahmetov, Z. M.

doi:10.1080/00387018908053945

Cited by 5 publications

(3 citation statements)

References 16 publications

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“…This does not only involve the Renner−Teller effect as discussed in this paper but also spin−orbit and derivative couplings between the adiabatic potential energy surfaces. There are crossings of the 4 A ‘ ‘ surface discussed in the previous paragraph and the 2 A ‘ and 2 A ‘ ‘ surfaces used in our calculations (see ref ). Because there are nonzero spin−orbit matrix elements between these states this could be an important non adiabatic pathway to N( 4 S) + CO(X 1 Σ + ).…”

Section: Discussionmentioning

confidence: 86%

Computational Studies of the Kinetics of the C + NO and O + CN Reactions

2003

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Thermal rate coefficients for the reactions C(3P) + NO(X2Π) → CN(X2Σ+) + O(3P), C(3P) + NO(X2Π) → CO(XΣ+) + N(2D), and O(3P) + CN(XΣ+) → CO(X1Σ+) + N(2D) in the temperature range from 5 to 5000 K have been obtained using quasiclassical trajectory calculations. Results are reported for two ab initio potential energy surfaces corresponding to states of 2 A‘ and 2 A‘ ‘ symmetry. Good agreement between calculated and experimental rate coefficients are obtained for the C + NO reactions for all temperatures, whereas the rate coefficient for the O + CN reaction at room temperature is larger than that found experimentally. The dynamics is considerably different on the two potential energy surfaces with the 2 A‘ ‘ giving rate coefficients in better agreement with experiments. The quality of the potential energy surfaces are discussed in the light of new electronic structure calculations including spin−orbit coupling.

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Section: Discussionmentioning

confidence: 86%

Computational Studies of the Kinetics of the C + NO and O + CN Reactions

2003

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“…Recent ab initio theoretical calculations have predicted these and higher energy bound and dissociative states . The corresponding NCO (X̃, Ã, and B̃) states have been observed experimentally, but there have been few theoretical investigations of these or the higher energy electronic states. ,,, A fairly low level molecular orbital calculation dating back to 1975 predicts transition energies and oscillator strengths for excitation to eight electronic states of NCO . The resulting NCO transition energies calculated for the Franck−Condon region agree well with experimental results for the Ã and B̃ states.…”

Section: Discussionmentioning

confidence: 99%

“…As determined by molecular orbital calculations and confirmed by experiment, the first excited state (A ˜2Σ + ) has a stronger N-CO bond than the ground state with a shortened bond length similar to that of free CN. 4,12,13 Several electronic configurations are predicted to be involved in the excitation to the second excited state (B ˜2Π), 14,15 one of which involves a transition (3π* r 2π) from a bonding molecular orbital to an antibonding molecular orbital 12 and results in a lengthened N-CO bond. 16 Dissociation from the B ˜state thus appears more likely than from the A ˜state.…”

Section: Introductionmentioning

confidence: 99%

The 193-nm Photodissociation of NCO

2001

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The 193-nm photolysis of the NCO radical has been investigated. NCO was generated from the reaction of CN + O 2 , where the CN was produced by 193-nm photolysis of C 2 N 2 close to the nozzle of a pulsed jet. A second 193-nm photon dissociated the NCO radical during the same laser pulse. At this photon energy both the N-CO and the NC-O bonds may break. N( 2 D, 2 P) and CO products have been detected using vacuum ultraviolet laser induced fluorescence. A direct measurement of the N( 2 D):N( 2 P) branching ratio yielded an upper limit of 72 ( 18. The CO vibrational distribution was modeled with prior distributions for each of the contributing channels with coproducts N( 4 S, 2 D, 2 P). Combination of the results from the prior model and the direct measurement yielded a branching ratio of N( 4 S):N( 2 D):N( 2 P) of ( 5.1 ( 1.8):(93.6 ( 4.8):(1.3 ( 0.3). For the N( 2 D) + CO product channel, the average energy disposal into product relative translation (8%) and CO vibration (24%) was determined, leaving 68% of the available energy to appear as CO rotation. This observation suggests that the geometry of the dissociating state of NCO is likely bent.

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Fast beam studies of NCO free radical photodissociation

Cyr

Continetti

Metz

et al. 1992

The Journal of Chemical Physics

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The spectroscopy and dissociation dynamics of the NC0 radical have been investigated by applying fast radical beam photodissociation spectroscopy to the 5 211 +X 211 electronic transition. Measurements of the photodissociation cross section as a function of dissociation wavelength show that even the lowest vibrational levels of the g 211 state predissociate. Analysis of fragment kinetic energy release reveals that the spin-forbidden N(4S) + CO('2+) products are produced exclusively until 20.3 kcal/mol above the origin, at which point, the spin-allowed N(20) + CO product channel becomes energetically accessible. The spin-allowed channel dominates above this threshold. By determining the location of this threshold, we obtain a new &f for NC0 of 30.5 f 1 kcal/mol, several kcal/mol lower than the previously accepted value.-"NSERC (Canada) 1967, Predoctoral Fellow.

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MINDO/3 CI Study of NCO Spectrum and the Chemiluminescent Reaction N + CO → NCO + h

Cited by 5 publications

References 16 publications

Computational Studies of the Kinetics of the C + NO and O + CN Reactions

Computational Studies of the Kinetics of the C + NO and O + CN Reactions

The 193-nm Photodissociation of NCO

Fast beam studies of NCO free radical photodissociation

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