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Vibrationally quantum-state-specific reaction dynamics of H atom abstraction by CN radical in solution

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Vibrationally quantum-state-specific reaction dynamics of H atom abstraction by CN radical in solution. / Greaves, S.J; Rose, R.A; Oliver, Thomas A.A.; Glowacki, D.R; Ashfold, M.N.R; Harvey, J.N; Clarke, I.P; Greetham, G.M; Parker, A.W; Towrie, M; Orr-Ewing, A.J.

In: Science, Vol. 331, No. 6023, 18.03.2011, p. 1423 - 1426.

Research output: Contribution to journalArticle

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Greaves, SJ, Rose, RA, Oliver, TAA, Glowacki, DR, Ashfold, MNR, Harvey, JN, Clarke, IP, Greetham, GM, Parker, AW, Towrie, M & Orr-Ewing, AJ 2011, 'Vibrationally quantum-state-specific reaction dynamics of H atom abstraction by CN radical in solution', Science, vol. 331, no. 6023, pp. 1423 - 1426. https://doi.org/10.1126/science.1197796

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Greaves, S.J ; Rose, R.A ; Oliver, Thomas A.A. ; Glowacki, D.R ; Ashfold, M.N.R ; Harvey, J.N ; Clarke, I.P ; Greetham, G.M ; Parker, A.W ; Towrie, M ; Orr-Ewing, A.J. / Vibrationally quantum-state-specific reaction dynamics of H atom abstraction by CN radical in solution. In: Science. 2011 ; Vol. 331, No. 6023. pp. 1423 - 1426.

Bibtex

@article{e93a00727c0d49b79d6737934f4c58a0,
title = "Vibrationally quantum-state-specific reaction dynamics of H atom abstraction by CN radical in solution",
abstract = "Solvent collisions can often mask initial disposition of energy to the products of solution-phase chemical reactions. Here, we show with transient infrared absorption spectra obtained with picosecond time resolution that the nascent HCN products of reaction of CN radicals with cyclohexane in chlorinated organic solvents exhibit preferential excitation of one quantum of the C-H stretching mode and up to two quanta of the bending mode. On time scales of approximately 100 to 300 picoseconds, the HCN products undergo relaxation to the vibrational ground state by coupling to the solvent bath. Comparison with reactions of CN radicals with alkanes in the gas phase, known to produce HCN with greater C-H stretch and bending mode excitation (up to two and approximately six quanta, respectively), indicates partial damping of the nascent product vibrational motion by the solvent. The transient infrared spectra therefore probe solvent-induced modifications to the reaction free energy surface and chemical dynamics.",
keywords = "Chemical Phenomena, Cyclohexanes, Free Radicals, Hydrogen, Hydrogen Cyanide, Kinetics, Models, Chemical, Physicochemical Processes, Solutions, Solvents, Spectrophotometry, Infrared",
author = "S.J Greaves and R.A Rose and Oliver, {Thomas A.A.} and D.R Glowacki and M.N.R Ashfold and J.N Harvey and I.P Clarke and G.M Greetham and A.W Parker and M Towrie and A.J Orr-Ewing",
year = "2011",
month = "3",
day = "18",
doi = "10.1126/science.1197796",
language = "English",
volume = "331",
pages = "1423 -- 1426",
journal = "Science",
issn = "0036-8075",
publisher = "American Association for the Advancement of Science",
number = "6023",

}

RIS - suitable for import to EndNote

TY - JOUR

T1 - Vibrationally quantum-state-specific reaction dynamics of H atom abstraction by CN radical in solution

AU - Greaves, S.J

AU - Rose, R.A

AU - Oliver, Thomas A.A.

AU - Glowacki, D.R

AU - Ashfold, M.N.R

AU - Harvey, J.N

AU - Clarke, I.P

AU - Greetham, G.M

AU - Parker, A.W

AU - Towrie, M

AU - Orr-Ewing, A.J

PY - 2011/3/18

Y1 - 2011/3/18

N2 - Solvent collisions can often mask initial disposition of energy to the products of solution-phase chemical reactions. Here, we show with transient infrared absorption spectra obtained with picosecond time resolution that the nascent HCN products of reaction of CN radicals with cyclohexane in chlorinated organic solvents exhibit preferential excitation of one quantum of the C-H stretching mode and up to two quanta of the bending mode. On time scales of approximately 100 to 300 picoseconds, the HCN products undergo relaxation to the vibrational ground state by coupling to the solvent bath. Comparison with reactions of CN radicals with alkanes in the gas phase, known to produce HCN with greater C-H stretch and bending mode excitation (up to two and approximately six quanta, respectively), indicates partial damping of the nascent product vibrational motion by the solvent. The transient infrared spectra therefore probe solvent-induced modifications to the reaction free energy surface and chemical dynamics.

AB - Solvent collisions can often mask initial disposition of energy to the products of solution-phase chemical reactions. Here, we show with transient infrared absorption spectra obtained with picosecond time resolution that the nascent HCN products of reaction of CN radicals with cyclohexane in chlorinated organic solvents exhibit preferential excitation of one quantum of the C-H stretching mode and up to two quanta of the bending mode. On time scales of approximately 100 to 300 picoseconds, the HCN products undergo relaxation to the vibrational ground state by coupling to the solvent bath. Comparison with reactions of CN radicals with alkanes in the gas phase, known to produce HCN with greater C-H stretch and bending mode excitation (up to two and approximately six quanta, respectively), indicates partial damping of the nascent product vibrational motion by the solvent. The transient infrared spectra therefore probe solvent-induced modifications to the reaction free energy surface and chemical dynamics.

KW - Chemical Phenomena

KW - Cyclohexanes

KW - Free Radicals

KW - Hydrogen

KW - Hydrogen Cyanide

KW - Kinetics

KW - Models, Chemical

KW - Physicochemical Processes

KW - Solutions

KW - Solvents

KW - Spectrophotometry, Infrared

U2 - 10.1126/science.1197796

DO - 10.1126/science.1197796

M3 - Article

VL - 331

SP - 1423

EP - 1426

JO - Science

JF - Science

SN - 0036-8075

IS - 6023

ER -