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    Collision Efficiency Parameter Influence on Pressure-Dependent Rate Constant Calculations Using the SS-QRRK Theory

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    Type
    Article
    Authors
    Grajales Gonzalez, Edwing
    Monge Palacios, Manuel
    Sarathy, Mani cc
    KAUST Department
    Chemical Engineering Program
    Clean Combustion Research Center
    Combustion and Pyrolysis Chemistry (CPC) Group
    Physical Science and Engineering (PSE) Division
    KAUST Grant Number
    OSR-2016-CRG5-3022
    Date
    2020-07-14
    Online Publication Date
    2020-07-14
    Print Publication Date
    2020-08-06
    Embargo End Date
    2021-07-14
    Permanent link to this record
    http://hdl.handle.net/10754/664291
    
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    Abstract
    The system-specific quantum Rice-Ramsperger-Kassel (SS-QRRK) theory [J. Am. Chem. Soc. 2016, 138, 2690] is suitable to determine rate constants below the high-pressure limit. Its current implementation allows incorporating variational effects, multi-dimensional tunneling, and multi-structural torsional anharmonicity in rate constant calculations. Master equation solvers offer more rigorous approach to compute pressure-dependent rate constant, but several implementations available in the literature do not incorporate the aforementioned effects. However, SS-QRRK theory coupled with a formulation of the modified strong collision model underestimates the value of unimolecular pressure-dependent rate constants in the high temperature regime for reactions involving large molecules. This underestimation is a consequence of the definition for collision efficiency, which is part of the energy transfer model. The selection of the energy transfer model and its parameters constitute a common issue in pressure-dependent calculations. To overcome this underestimation problem, we evaluated and implemented in a bespoke Python code two alternative definitions for the collision efficiency using the SS-QRRK theory, and tested their performance by comparing the pressure-dependent rate constants with Rice-Ramsperger-Kassel-Marcus/Master Equation (RRKM/ME) results. The modeled systems were the tautomerization of propen-2-ol and the decomposition of 1-propyl, 1-butyl, and 1-pentyl radicals. One of the tested definitions, which Dean et al. explicitly derived [Z. Phys. Chem. 2000, 214, 1533], corrected the underestimation of the pressure-dependent rate constants and, in addition, qualitatively reproduced the trend of RRKM/ME data. Therefore, the used SS-QRRK theory with accurate definitions for the collision efficiency can yield results that are in agreement with those from more sophisticated methodologies such as RRKM/ME.
    Citation
    Grajales-González, E., Monge-Palacios, M., & Sarathy, S. M. (2020). Collision Efficiency Parameter Influence on Pressure-Dependent Rate Constant Calculations Using the SS-QRRK Theory. The Journal of Physical Chemistry A. doi:10.1021/acs.jpca.0c02943
    Sponsors
    This work was supported by King Abdullah University of Science and Technology (KAUST), Office of Sponsored Research (OSR) under Award No. OSR-2016-CRG5-3022. We appreciate the resources of the Supercomputing Laboratory at KAUST.
    Publisher
    American Chemical Society (ACS)
    Journal
    The Journal of Physical Chemistry A
    DOI
    10.1021/acs.jpca.0c02943
    Additional Links
    https://pubs.acs.org/doi/10.1021/acs.jpca.0c02943
    ae974a485f413a2113503eed53cd6c53
    10.1021/acs.jpca.0c02943
    Scopus Count
    Collections
    Articles; Physical Science and Engineering (PSE) Division; Chemical Engineering Program; Clean Combustion Research Center

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