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Zeitschrift für Physikalische Chemie

International journal of research in physical chemistry and chemical physics

Editor-in-Chief: Rademann, Klaus


IMPACT FACTOR 2018: 0.975
5-year IMPACT FACTOR: 1.021

CiteScore 2018: 1.20

SCImago Journal Rank (SJR) 2018: 0.327
Source Normalized Impact per Paper (SNIP) 2018: 0.391

Online
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2196-7156
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Volume 229, Issue 10-12

Issues

Determination of the Temperature-Dependent OH (H2O) + CH3I Rate Constant by Experiment and Simulation

Jing Xie
  • Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, Texas 79409-1061, USA
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/ Michael J. Scott
  • Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, Texas 79409-1061, USA
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/ William L. Hase
  • Corresponding author
  • Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, Texas 79409-1061, USA
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/ Peter M. Hierl / Albert A. Viggiano
  • Air Force Research Laboratory, Space Vehicles Directorate, Kirtland AFB, New Mexico 87117-5776, USA
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Published Online: 2015-10-02 | DOI: https://doi.org/10.1515/zpch-2015-0663

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.

Keywords: Direct Dynamics; Micro-Solvation; SN2; Proton Transfer; SIFT; Zero Point Energy

About the article

Accepted: 2015-08-20

Received: 2015-07-23

Published Online: 2015-10-02

Published in Print: 2015-10-28


Citation Information: Zeitschrift für Physikalische Chemie, Volume 229, Issue 10-12, Pages 1747–1763, ISSN (Online) 2196-7156, ISSN (Print) 0942-9352, DOI: https://doi.org/10.1515/zpch-2015-0663.

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