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

Research output: Contribution to journalArticle

Original languageEnglish
Pages (from-to)1423 - 1426
Number of pages4
Issue number6023
DatePublished - 18 Mar 2011


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.

    Research areas

  • Chemical Phenomena, Cyclohexanes, Free Radicals, Hydrogen, Hydrogen Cyanide, Kinetics, Models, Chemical, Physicochemical Processes, Solutions, Solvents, Spectrophotometry, Infrared

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  • CN + cyclohexane Science 2011

    Rights statement: Science 18 March 2011: Vol. 331 no. 6023 pp. 1423-1426 DOI: 10.1126/science.1197796

    Submitted manuscript, 538 KB, PDF document


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