Vibrationally Quantum-State–Specific Reaction Dynamics of H Atom Abstraction by CN Radical in Solution

Greaves, Stuart J.; Rose, Rebecca; Oliver, Thomas A. A.; Glowacki, David R.; Ashfold, Michael N. R.; Harvey, Jeremy N.; Clark, Ian P.; Greetham, Gregory M.; Parker, Anthony W.; Towrie, Michael; Orr-Ewing, Andrew J.

doi:10.1126/science.1197796

Cited by 76 publications

(146 citation statements)

References 25 publications

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“…Detailed descriptions of the laser-based instruments and the sample preparation and handling procedures are presented elsewhere, [58][59][60] and we provide only a brief summary here. Grade) before use.…”

Section: Methodsmentioning

confidence: 99%

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: Methodsmentioning

confidence: 99%

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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“…The details of each system and our experimental methods have been described previously, 19,28 therefore only a brief description relating directly to the current study is provided here.…”

Section: Methodsmentioning

confidence: 99%

“…[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: 95%

“…33 We estimate that approximately 30% dichloromethane. [17][18][19][20][21] Assignment to CH2CN (or CD2CN) products of reaction (2) was discounted because we conducted experiments on the UV photolysis of ICH2CN in acetonitrile and did not observe the same spectral features. DFT calculations also fail to predict CH2CN / CD2CN bands in proximity to the observed features and with the correct isotope shifts.…”

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

confidence: 99%

“…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%

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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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Empirical Valence Bond Methods for Exploring Reaction Dynamics in the Gas Phase and in Solution

Harvey

O’Connor

Glowacki

2017

Theory and Applications of the Empirical Valence Bond Approach

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Vibrationally Quantum-State–Specific Reaction Dynamics of H Atom Abstraction by CN Radical in Solution

Abstract: Molecular vibrations in a solution-phase reaction are detected at a level of detail rivaling that of gas-phase studies.

Cited by 76 publications

References 25 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

Empirical Valence Bond Methods for Exploring Reaction Dynamics in the Gas Phase and in Solution

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