2074-87-5Relevant academic research and scientific papers
XCN (X=Cl, Br and I): a novel source of isocyanogen
Blanch, Rodney J.,McCluskey, Adam
, p. 116 - 120 (1995)
Ambient light photolysis of gaseous BrCN, ClCN, and ICN results in the production of isocyanogen (NCNC) as the sole CN containing product. The flash vacuum pyrolysis of BrCN (1100°C and E-5 mbar) generates NCNC, NCCN, HOCN, HNCO and the CN radical.
Kinetics of the NCN + NO reaction over a broad temperature and pressure range
Welz, Oliver,Olzmann, Matthias
, p. 7293 - 7301 (2012/09/22)
Rate coefficients for the reaction 3NCN + NO → products (R3) were measured in the temperature range 251-487 K at pressures from 10 mbar up to 50 bar with helium as the bath gas. The experiments were carried out in slow-flow reactors by using pu
Halogenated xenon cyanides ClXeCN, ClXeNC, and BrXeCN
Arppe, Teemu,Khriachtchev, Leonid,Lignell, Antti,Domanskaya, Alexandra V.,Raesaenen, Markku
, p. 4398 - 4402 (2012/05/31)
We report on the preparation and characterization of three new noble-gas molecules ClXeCN, ClXeNC, and BrXeCN. These molecules are synthesized by 193 nm photolysis and thermal annealing of ClCN and BrCN in a xenon matrix. The absorption spectra are measured in the mid- and far-infrared regions, and the assignment is supported by isotope substitution and quantum chemical calculations at the B3LYP and MP2 levels of theory. The present results demonstrate a way to prepare other noble-gas molecules of this type.
Kinetics of the CCO + NO and CCO + NO2 reactions
Thweatt, W. David,Erickson, Mark A.,Hershberger, John F.
, p. 74 - 79 (2007/10/03)
The kinetics of the reaction of CCO radicals with NO and NO2 were studied using time-resolved infrared diode laser absorption spectroscopy. The rate constants were determined to be kCCO+NO = (5.36 ± 0.5) × 10-11 and k
Treatment of the K-quantum number in unimolecular reaction theory: Insights from product correlations
McGivern, W. Sean,North, Simon W.
, p. 14472 - 14477 (2007/10/03)
The connection between the K-quantum number and product correlations in the barrierless unimolecular dissociation of symmetric-top molecules is explored to establish a qualitative diagnostic for the treatment of the K-rotor dynamics in unimolecular reaction theory. We find that fragment scalar and vector correlations can provide guidance in this matter, and the photodissociation dynamics of thermal NCNO to form CN and NO at several dissociation wavelengths are presented to demonstrate the utility of this approach. The goodness of the K-quantum number can be related to the amount of energy in the conserved vibrational modes at the inner transition state. On the basis of measured correlated vibrational distributions, the K-quantum number is found to be approximately conserved at the inner transition state for the photodissociation of NCNO at 514, 520, and 526 nm. The methodology, involving a comparison of product distributions from the photodissociation of jet and thermal ensembles at identical wavelengths, is general and may be applied to previously studied systems that dissociate along barrierless potential energy surfaces, CF3NO and CH2CO. In addition, vector correlations serve as a means to probe the K-mixing at the outer transition state, and measured v-j correlations in the photodissociation of thermal NCNO are presented.
Probing the nature of the K-rotor in unimolecular reactions: Scalar and vector correlations in the photodissociation of NCNO
McGivern, W. Sean,North, Simon W.
, p. 7027 - 7034 (2007/10/03)
The photodissociation of NCNO at 520 and 532 nm was examined using transient frequency modulation Doppler spectroscopy in order to study vector and scalar correlations in the dissociation. A small correlation between v and J was observed corresponding to Β00(22) bipolar moments ranging from 0.00±0.02 to -0.03±0.02 at 532 nm and 0.00±0.02 to -0.01±0.02 at 520 nm. These were well described by a helicity unrestricted PST formulation at both wavelengths.
Channeling of products in the hot atom reaction H + (CN)2 → HCN/HNC + CN and in the reaction of CN with CH3SH
Decker, Brian K.,Macdonald, R. Glen
, p. 6817 - 6825 (2007/10/03)
Infrared transient absorption spectroscopy was used to determine the total product branching fractions for the gas-phase hot atom reaction H + (CN)2 → HCN/HNC + CN (a) and the reaction CN + CH3SH → HCN/HNC + CH3S/CH2SH (b) at 293 K. The reactive H atoms had an initial mean translational energy of 92 kJ mol-1, with a 38 kJ mol-1 fwhm Gaussian energy distribution. The branching fractions determined for the product channels forming HCN and HNC, respectively, are 0.88 and 0.12 (±0.05) for reaction (a) and 0.81 and 0.19 (±0.08) for reaction (b). The bimolecular rate constant for reaction (b) was measured to be (2.7 ± 0.3) × 10-10 cm3 molec-1 s-1 at 293 K. The observed product branching fractions for reaction (a) are consistent with the assumption that the average reactive cross sections for the two product channels are approximately equal above their respective energy thresholds. The results for reaction (a) are compared with the related H + XCN (X = Br, Cl) reactions. The large rate coefficient for reaction (b) suggests an interaction via a long-range intermolecular potential, which is facilitated by the small ionization energy of CH3SH and large electron affinity of CN. The results for reaction (b) are compared with the related reactions of Cl and OH with CH3SH.
Energy disposal in CN(X 2Σ+) produced in the 157 nm photodissociation of acrylonitrile
Guo,Carrington,Filseth
, p. 8411 - 8417 (2007/10/03)
The rovibrational population distribution for the CN(X) fragment produced in the 157.6 nm photodissociation of acrylonitrile was measured. It was observed that the average energies in vibration and rotation of CN were approximately equal and represented about 5% of the available energy with vinyl radical as the co-fragment. It was suggested that dynamical factors played a significant role in energy disposal as the vibrational and rotational distributions were not in good agreement with an energy-conserving prior distribution.
Kinetics of the C2(a3IIu) radical reacting with selected molecules and atoms
Becker,Donner,Freitas Dinis,Geiger,Schmidt,Wiesen
, p. 503 - 517 (2007/10/03)
Rate coefficients for reactions of the C2 radical in its a3IIu electronic state with H, N and O atoms and with C3O2, C4F6, H2, NO, N2O, C2H2, C2H4, C3 H4 and C6H6 were determined. This work represents the first study of reactions of C2(a3IIu) radicals with the atoms investigated at room temperature and 4 Torr total pressure. The bimolecular rate constants obtained for the atom reactions were kc2+o = (9.8 ± 1.0) × 10-11- , kc2+N = (2.8 ±1.0) × 10-11 and kc2+N-14, in units of cm3 s-1. In addition, the reaction C2 + O was found to be independent of total pressure in the range 2-60 Torr. For the reaction C2(a3IIu) + ethene (C2H4) a temperature and pressure independent rate constant of (9.5 × 1.2) × 10-11 cm3 s-1 was obtained in the temperature range 298-1000 K at 100 Torr total pressure and in the pressure range 5-100 Torr at 298 K. The following rate constants were determined at room temperature and a total pressure of 4 Torr for the reactions of C2(a3IIu) radicals with benzene (C6H6), acetylene (C2H2) and allene (C3H4): kc2+C6H6 = (4.9 ± 0.1) ×10-10, kc2+C2H2 = (1.0 ± 0.1) ± 10-10 and kc2+C3H4 = (1.9 ± 0.3) ×10-10, in units of cm3 s-1. The reaction C2 + NO was investigated at room temperature and 100 Torr total pressure, a rate constant kc2+NO = (6.8 ± 0.3) × 10-11 cm3 s-1 was obtained. The reaction C2 + N2O was studied at 4 Torr total pressure in the temperature range 300-700 K for which a temperature independent rate constant kc2+N2O = (3.1 ± 0.4)X 10-14 cm3 s-1 was determined. by Oldenbourg Wissenschaftsverlag, Muenchen.
Experimental and theoretical determination of the magnetic dipole transition moment for the Br(4p5)(2P1/2←2P3/2) fine-structure transition and the quantum yield of Br(2P1/2) from the 193 nm photolysis of BrCN
He,Seth, Michael,Tokue,Macdonald, R. Glen
, p. 7821 - 7831 (2007/10/03)
The integrated-absorption coefficients of several hyperfine lines of the magnetic dipole allowed transition of the bromine atom, Br, center at 3685.2 cm-1 were measured, and a value for the square of the magnetic dipole transition moment of the Br atom was determined. A theoretical calculation for the magnetic dipole transition moment was also carried out using a relativistic ab initio atomic structure formulation. The theoretical value was in excellent agreement with the value predicted assuming pure LS coupling, and in reasonable agreement with experiment. The Br atom was generated in equal concentration with the cyano radical (CN) by the 193 nm photolysis of cyanogen bromine, BrCN. The CN radicals were titrated by the rapid reaction with C3H8 to generate HCN and a small amount of HNC. Both time-resolved and frequency-scanned infrared absorption spectroscopy were used to monitor the Br, HCN, and HNC species. The photolysis of BrCN at 193 nm produced both the ground state Br(2P3/2) and the spin-orbit excited Br(2P1/2) atoms, and the yield for the production of Br(2P1/2) atoms was measured to be 0.31±0.01. The rate constants for the quenching of Br(2P1/2) by BrCN and C3H8 at 293 K were also determined.
