Determination of the Temperature-Dependent OH− (H2O) + CH3I Rate Constant by Experiment and Simulation
-
Jing Xie
,
Peter M. Hierl
Abstract
Experimental and simulation studies of the OH–(H2O) + CH3I reaction give temperature dependent rate constants which are in excellent agreement. Though there are statistical uncertainties, there is an apparent small decrease in the rate constant as the temperature is increased from − 60 to 125 ℃, and for this temperature range the rate constant is ∼ 1.6 times smaller than that for the unsolvated reactants OH– + CH3I. Previous work [J. Phys. Chem. A 117 (2013) 14019] for the unsolvated reaction found that the SN2 and proton transfer pathways, forming CH3OH + I– and CH2I– + H2O, have nearly equal probabilities. However, for the microsolvated OH–(H2O) + CH3I reaction the SN2 pathways dominate. An important contributor to this effect is the stronger binding of H2O to the OH– reactant than to the proton transfer product CH2I–, increasing the barrier for the proton transfer pathway. The effect of microsolvation on the rate constant for the OH–(H2O)0,1 + CH3I reactions agrees with previous experimental studies for X–(H2O)0,1 + CH3Y reactions. The simulations show that there are important non-statistical attributes to the entrance- and exit-channel dynamics for the OH–(H2O) + CH3I reaction.
Acknowledgement
The computational research reported here is based upon work supported by the Robert A. Welch Foundation under grant No. D-0005. The simulations were performed at the High Performance Computing Center (HPCC) at Texas Tech University, under the direction of Philip W. Smith, and on the Robinson computer cluster in the TTU Department of Chemistry and Biochemistry whose purchase was funded by the National Science Foundation CRIF-MU Grant CHE-0840493. The experimental research is supported by the Air Force Office of Scientific Research through the AFOSR-2303EP grant to A. A. Viggiano. Bill Hase and Al Viggiano have greatly appreciated and enjoyed their interactions with Juergen Troe regarding the dynamics and kinetics of chemical reactions, and in particular unimolecular reactions.
©2015 Walter de Gruyter Berlin/Boston
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- Frontmatter
- Preface
- Congratulations to Jürgen Troe
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Artikel in diesem Heft
- Frontmatter
- Preface
- Congratulations to Jürgen Troe
- The Kinetics of the Reaction C2H5• + HI → C2H6 + I• over an Extended Temperature Range (213–623 K): Experiment and Modeling
- Collisional Relaxation of NCN: An Experimental Study with Laser-Induced Fluorescence
- Reaction of Chlorine Molecules with Unsaturated Submicron Organic Particles
- Theoretical Kinetics Study of the Reactions Forming the ClCO Radical Cycle in the Middle Atmosphere of Venus
- On the Relation between Population Kinetics and State-to-State Rate Coefficients for Vibrational Energy Transfer
- Investigation of the ν2 + 2ν3 Subband in the Overtone Icosad of 13CH4 by Pulsed Supersonic Jet and Diode Laser Cavity Ring-Down Spectroscopy: Partial Rovibrational Analysis and Nuclear Spin Symmetry Conservation
- The Rotationally-Resolved Absorption Spectrum of Formaldehyde from 6547 to 7051 cm−1
- Constraining the Conformational Landscape of a Polyether Building Block by Raman Jet Spectroscopy
- The Reaction Kinetics of Amino Radicals with Sulfur Dioxide
- Challenging High-Level ab initio Rovibrational Spectroscopy: The Nitrous Oxide Molecule
- Reaction of the CF3 Radical with Various Cations (Ar+, Xe+, O2+, NO+, CO2+, C2F5+)
- Electronic Spectra of Corannulenic Cations and Neutrals in Neon Matrices and Protonated Corannulene in the Gas Phase at 15 K
- Photoionization Yields in Intense fs-Laser Fields – A Systematic Investigation of Chirp Effects
- Determination of the Temperature-Dependent OH− (H2O) + CH3I Rate Constant by Experiment and Simulation
- Can we Observe Gas Phase Nucleation at the Molecular Level?
- Multiphoton Ionization of Liquid-to-Supercritical Methanol. Ultrafast Dynamics of Electron Localization and Geminate Recombination
- Femtosecond Infrared Spectroscopy of Aroylperoxide Photofragmentation – Site Selective Decarboxylation
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- Complexation and Chiral Recognition of Chiral Binaphthyl Derivatives and β-Cyclodextrins in Solution Probed by Triplet Excited State Relaxation
- Ionic Solutions Probed by Resonant Inelastic X-ray Scattering
- Ordering Phenomena in Surfactant Systems: From Micellar Solutions to Gel and Crystalline Phases
- Investigation of the Growth Behaviour of Cobalt Thin Films from Chemical Vapour Deposition, Using Directly Coupled X-ray Photoelectron Spectroscopy
- Ultrafast Dynamics of the Indoline Dye D149 on Mesoporous ZnO and Al2O3 Thin Films
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