General Effect of van der Waals Interactions on the Stability of Alkoxy Intermediates on Metal Surfaces

Journal Article · Wed Jul 19 00:00:00 EDT 2017 · Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry

DOI:https://doi.org/10.1021/acs.jpcb.7b04952· OSTI ID:1480287

Xu, Yunfei ^[1]; Chen, Wei ^[2]; Kaxiras, Efthimios ^[2]; Friend, Cynthia M.  ^[3]; Madix, Robert J. ^[4]

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1. Harvard Univ., Cambridge, MA (United States). Dept. of Chemistry and Chemical Biology
2. Harvard Univ., Cambridge, MA (United States). Dept. of Physics; Harvard Univ., Cambridge, MA (United States). Harvard John A. Paulson School of Engineering and Applied Sciences
3. Harvard Univ., Cambridge, MA (United States). Dept. of Chemistry and Chemical Biology; Harvard Univ., Cambridge, MA (United States). Harvard John A. Paulson School of Engineering and Applied Sciences
4. Harvard Univ., Cambridge, MA (United States). Harvard John A. Paulson School of Engineering and Applied Sciences

The critical role of noncovalent van der Waals (vdW) interactions in determining the relative thermodynamic stability of alkoxy intermediates has been demonstrated for the Cu(110) surface using a combination of experiment and theory. The results may be significant for the selectivity control of copper-based reactions of alcohols. Previous examination of this effect on Au(110) was also extended to include higher molecular weight alcohols; on Cu(110) and Au(110) the hierarchy for the strength of binding of the alkoxys was found to be the same within experimental accuracy, with alkoxy species of greater chain length being more stable. The equilibrium constants governing the competition of alcohol pairs for binding sites of the alkoxys are also similar on the two surfaces. These results reveal the generality of such vdW effects. In conclusion, this work expands the understanding of the role of vdW interactions on the binding efficacy of key reactive intermediates on metal surfaces, a key factor in the rational design of complex and selective catalytic processes.

• Research Organization: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Energy Frontier Research Centers (EFRC) (United States). Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC)
• Sponsoring Organization: USDOE Office of Science (SC), Basic Energy Sciences (BES)
• Grant/Contract Number: SC0012573
• OSTI ID: 1480287
• Journal Information: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry, Vol. 122, Issue 2; ISSN 1520-6106
• Publisher: American Chemical Society
• Country of Publication: United States
• Language: English

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