Vibrationally quantum-state-specific dynamics of the reactions of CN radicals with organic molecules in solution

Rose, Rebecca; Greaves, Stuart J.; Oliver, Thomas A. A.; Clark, Ian P.; Greetham, Gregory M.; Parker, Anthony W.; Towrie, Michael; Orr-Ewing, Andrew J.

doi:10.1063/1.3603966

Cited by 21 publications

(66 citation statements)

References 34 publications

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“…[37][38][39][40][41][42] The interpretation of these experimental measurements has been supported by simulations of the dissociation dynamics and fates of the I and CN fragments. 41,[43][44][45][46][47][48][49] Rivera et al 39 reported a peaked feature centred at 390 nm in the UV/visible absorption spectrum after photolysis of ICN in water and ethanol that closely resembled a low resolution gas-phase BX spectrum of the CN radical.…”

Section: Introductionmentioning

confidence: 69%

“…4(d), were supplemented by spectra of the type we have reported previously in the C-H stretching (3) region around 3260 cm -1 for other reactions. [41][42] In this region, C-H stretching excitation shifts the IR absorption bands of HCN by close to -100 cm -1 relative to the fundamental band for each additional quantum of vibration. HCN that is vibrationally excited in the C-H mode can therefore be clearly distinguished from ground vibrational level molecules in the TVAS data.…”

Section: Reaction Of Cn Radicals With Dichloromethanementioning

confidence: 97%

“…4(f)). The assignments of bands in spectra obtained in chlorinated solvents have been considered previously, 42 and provide guidance for interpretation of spectra in other solvents. Fig.…”

Section: Transient Vibrational Absorption Spectroscopy Of Photoexcitementioning

confidence: 99%

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Recombination, Solvation and Reaction of CN Radicals Following Ultraviolet Photolysis of ICN in Organic Solvents

Coulter¹,

Grubb²,

Koyama³

et al. 2015

J. Phys. Chem. A

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Section: Introductionmentioning

confidence: 69%

Section: Reaction Of Cn Radicals With Dichloromethanementioning

confidence: 97%

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Recombination, Solvation and Reaction of CN Radicals Following Ultraviolet Photolysis of ICN in Organic Solvents

Coulter¹,

Grubb²,

Koyama³

et al. 2015

J. Phys. Chem. A

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“…[17][18][19][20][21][33][34][35][36] This assignment is further supported by the fact there is no isotope shift when CH3CN is replaced by CD3CN. The INC(v=0) band grows with a time constant of 7.7 ± 0.7 ps in CH3CN that is commensurate with the loss of CN seen by TEAS with  = 8.5  2.1 ps, followed by a more gradual increase with a time constant of 341 ± 21 ps.…”

Section: Tvas Of Solutions Of Icn In Ch3cn Following 267 Nm Excitationmentioning

confidence: 94%

“…Complete quenching of nascent vibrational excitation by interaction with the solvent bath can take tens to hundreds of picoseconds in chloroform and dichloromethane solutions. 4,5,[17][18][19]22 Modifications of the reaction mechanism by interactions with the solvent bath include formation of complexes between CN radicals and solvent molecules. 23,24 The current study extends these prior investigations to reactions of CN radicals in acetonitrile (CH3CN or CD3CN), which is chosen because it is a more strongly interacting solvent than chloroform and dichloromethane.…”

Section: Introductionmentioning

confidence: 99%

Reaction Dynamics of CN Radicals in Acetonitrile Solutions

et al. 2015

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General rightsThis document is made available in accordance with publisher policies. Please cite only the published version using the reference above. Full terms of use are available: http://www.bristol.ac.uk/pure/about/ebr-terms Time-resolved electronic absorption spectroscopy (TEAS) in the ultraviolet and visible spectral regions observes rapid production and loss (with a decay time constant of 0.6  0.1 ps) of the photolytically generated free CN radicals. Some of these radicals convert to a solvated form which decays with a lifetime of 8.5  2.1 ps. Time-resolved vibrational absorption spectroscopy (TVAS) reveals that the free and solvated CN-radicals undergo geminate recombination with I atoms to make ICN and INC, H-atom abstraction reactions, and addition reactions to solvent molecules to make C3H3N2 radical species. These radical products have a characteristic absorption band at 2036 cm -1 that shifts to 2010 cm -1 when ICN is photolysed in CD3CN. The HCN yield is low, suggesting the addition pathway competes effectively with Hatom abstraction from CH3CN, but the delayed growth of the C3H3N2 radical band is best described by reaction of solvated CN radicals through an unobserved intermediate species.Addition of methanol or tetrahydrofuran as a co-solute promotes H-atom abstraction reactions that produce vibrationally hot HCN. The combination of TEAS and TVAS measurements shows that the rate-limiting process for production of ground-state HCN is vibrational cooling, the rate of which is accelerated by the presence of methanol or tetrahydrofuran.

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Mechanisms for the Breakdown of Halomethanes through Reactions with Ground‐State Cyano Radicals

et al. 2014

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ARTICLE Mechanisms for Breakdown of Halomethanes through Reactions with Ground State Cyano RadicalsPooria Farahani, [a] Satoshi Maeda, [b] Joseph S. Francisco, [c] and Marcus Lundberg* , [a] Abstract: One route to break down halomethanes is through reactions with radical species. The capability of the Artificial Force Induced Reaction (AFIR) algorithm to efficiently explore a large number of radical reaction pathways has been illustrated for reactions between haloalkanes CX3Y (X= H,F; Y=Cl,Br) and ground state ( 2 Σ + ) cyano radicals (CN). For CH3Cl + CN 71 stationary points in eight different pathways have been located and, in agreement with experiment, the highest rate constant (10 8 s -1 M -1 at 298 K) is obtained for hydrogen abstraction. In CH3Br the rate constants for hydrogen and halogen abstraction are similar (10 9 s -1 M -1 ) while replacing hydrogen with fluorine eliminates the hydrogen abstraction route and decreases the rate constants for halogen abstraction by 2-3 orders of magnitude. The detailed mapping of stationary points opens up for accurate calculations of product distributions and the encouraging rate constants motivate future studies with other radicals.

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Vibrationally quantum-state-specific dynamics of the reactions of CN radicals with organic molecules in solution

Cited by 21 publications

References 34 publications

Recombination, Solvation and Reaction of CN Radicals Following Ultraviolet Photolysis of ICN in Organic Solvents

Recombination, Solvation and Reaction of CN Radicals Following Ultraviolet Photolysis of ICN in Organic Solvents

Reaction Dynamics of CN Radicals in Acetonitrile Solutions

Mechanisms for the Breakdown of Halomethanes through Reactions with Ground‐State Cyano Radicals

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