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Title: Effect of Frustrated Rotations on the Pre-Exponential Factor for Unimolecular Reactions on Surfaces: A Case Study of Alkoxy Dehydrogenation

Abstract

If theory is to be able to predict the rates of catalytic reactions over extended ranges of temperature and pressure, it must provide accurate rate constants for elementary reaction steps, including both the activation energy and pre-exponential factor. A standing difficulty with this objective is the treatment of floppy modes in the partition function for the adsorbed species. This issue leads to limited accuracy in the pre-exponential factor computed for realistic systems. Here we investigate the C–H bond breaking for a series of linear-chain alkoxides on Cu(110) using density functional theory, since the results can be compared to experimental data for the rate constants. The structural similarity of these species enables us to understand the systematic effect of molecular size on the frustrated motions and pre-exponential factor. First, we discuss the complexities of finding the global minimum structure of the adsorbed species and highlight the high dimensionality of configuration space to be sampled. Then, we analyze the motions of harmonic normal modes, including the motions of the underlying metal atoms, and compute the harmonic pre-exponential factors. To account for periodic frustrated rotations we use the hindered rotor model: this motion significantly decreases the pre-exponential factor in the C–H bond breaking,more » the effect increasing with molecular size. We also estimate the anharmonic effect using the Morse treatment of potentials. The activation energy and pre-exponential factor computed for CH3O are in excellent quantitative agreement with experiment. Finally, the trends computed for the homologous series of alcohols are also reflected by experiment.« less

Authors:
ORCiD logo [1];  [1]; ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Harvard Univ., Cambridge, MA (United States)
  2. Univ. of California, Los Angeles, CA (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC); Harvard Univ., Cambridge, MA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1595062
Grant/Contract Number:  
SC0012573
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 124; Journal Issue: 2; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Chen, Wei, Sun, Lixin, Kozinsky, Boris, Friend, Cynthia M., Kaxiras, Efthimios, Sautet, Philippe, and Madix, Robert J. Effect of Frustrated Rotations on the Pre-Exponential Factor for Unimolecular Reactions on Surfaces: A Case Study of Alkoxy Dehydrogenation. United States: N. p., 2019. Web. https://doi.org/10.1021/acs.jpcc.9b10017.
Chen, Wei, Sun, Lixin, Kozinsky, Boris, Friend, Cynthia M., Kaxiras, Efthimios, Sautet, Philippe, & Madix, Robert J. Effect of Frustrated Rotations on the Pre-Exponential Factor for Unimolecular Reactions on Surfaces: A Case Study of Alkoxy Dehydrogenation. United States. https://doi.org/10.1021/acs.jpcc.9b10017
Chen, Wei, Sun, Lixin, Kozinsky, Boris, Friend, Cynthia M., Kaxiras, Efthimios, Sautet, Philippe, and Madix, Robert J. Sun . "Effect of Frustrated Rotations on the Pre-Exponential Factor for Unimolecular Reactions on Surfaces: A Case Study of Alkoxy Dehydrogenation". United States. https://doi.org/10.1021/acs.jpcc.9b10017. https://www.osti.gov/servlets/purl/1595062.
@article{osti_1595062,
title = {Effect of Frustrated Rotations on the Pre-Exponential Factor for Unimolecular Reactions on Surfaces: A Case Study of Alkoxy Dehydrogenation},
author = {Chen, Wei and Sun, Lixin and Kozinsky, Boris and Friend, Cynthia M. and Kaxiras, Efthimios and Sautet, Philippe and Madix, Robert J.},
abstractNote = {If theory is to be able to predict the rates of catalytic reactions over extended ranges of temperature and pressure, it must provide accurate rate constants for elementary reaction steps, including both the activation energy and pre-exponential factor. A standing difficulty with this objective is the treatment of floppy modes in the partition function for the adsorbed species. This issue leads to limited accuracy in the pre-exponential factor computed for realistic systems. Here we investigate the C–H bond breaking for a series of linear-chain alkoxides on Cu(110) using density functional theory, since the results can be compared to experimental data for the rate constants. The structural similarity of these species enables us to understand the systematic effect of molecular size on the frustrated motions and pre-exponential factor. First, we discuss the complexities of finding the global minimum structure of the adsorbed species and highlight the high dimensionality of configuration space to be sampled. Then, we analyze the motions of harmonic normal modes, including the motions of the underlying metal atoms, and compute the harmonic pre-exponential factors. To account for periodic frustrated rotations we use the hindered rotor model: this motion significantly decreases the pre-exponential factor in the C–H bond breaking, the effect increasing with molecular size. We also estimate the anharmonic effect using the Morse treatment of potentials. The activation energy and pre-exponential factor computed for CH3O are in excellent quantitative agreement with experiment. Finally, the trends computed for the homologous series of alcohols are also reflected by experiment.},
doi = {10.1021/acs.jpcc.9b10017},
journal = {Journal of Physical Chemistry. C},
number = 2,
volume = 124,
place = {United States},
year = {2019},
month = {12}
}

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