Hydrocarbon adsorption in an aqueous environment: A computational study of alkyls on Cu(111)

Matthew M. Montemore; Oliviero Andreussi; J. Will Medlin

doi:10.1063/1.4961027

journal article Aug 19, 2016

Hydrocarbon adsorption in an aqueous environment: A computational study of alkyls on Cu(111)

Matthew M. Montemore

Oliviero Andreussi J. Will Medlin

The Journal of Chemical Physics Vol. 145 No. 7 · AIP Publishing

View at Publisher Save 10.1063/1.4961027

Abstract

Hydrocarbon chains are important intermediates in various aqueous-phase surface processes, such as CO2 electroreduction, aqueous Fischer-Tropsch synthesis, and aqueous phase reforming of biomass-derived molecules. Further, the interaction between water and adsorbed hydrocarbons represents a difficult case for modern computational methods. Here, we explore various methods for calculating the energetics of this interaction within the framework of density functional theory and explore trade-offs between the use of low water coverages, molecular dynamics approaches, and minima hopping for identification of low energy structures. An effective methodology for simulating low temperature processes is provided by using a unit cell in which the vacuum space is filled with water, employing the minima hopping algorithm to search for low-lying minima, and including dispersion (van der Waals) interactions. Using this methodology, we show that a high coverage of adsorbed alkyls is destabilized by the presence of water, while a low coverage of alkyls is stabilized. Solvation has a small effect on the energetics of hydrocarbon chain growth, generally decreasing its favorability at low temperatures. We studied higher temperatures by running molecular dynamics simulations starting at the minima found by the minima hopping algorithm and found that increased temperatures facilitate chain growth. The self-consistent continuum solvation method effectively describes the alkyl-water interaction and is in general agreement with the explicit solvation results in most cases, but care should be taken at high alkyl coverage.

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References

Details

Published: Aug 19, 2016
Vol/Issue: 145(7)

Authors

M

Matthew M. Montemore

University of Colorado Boulder 1 Department of Mechanical Engineering, , UCB 427, Boulder, Colorado 80309, USA; University of Colorado Boulder 2 Department of Chemical and Biological Engineering, , UCB 596, Boulder, Colorado 80309, USA

O

Oliviero Andreussi

Università della Svizzera Italiana 3 Faculty of Informatics, Institute of Computational Science, , Via G. Buffi 13, 6904 Lugano, Switzerland; École Polytechnique Fédérale de Lausanne 4 Theory and Simulations of Materials (THEOS) and National Center for Computational Design and Discovery of Novel Materials (MARVEL), , Station 12, 1015 Lausanne, Switzerland

J

J. Will Medlin

University of Colorado Boulder 2 Department of Chemical and Biological Engineering, , UCB 596, Boulder, Colorado 80309, USA

Funding

National Science Foundation Award: CBET-0854251

Cite This Article

Matthew M. Montemore, Oliviero Andreussi, J. Will Medlin (2016). Hydrocarbon adsorption in an aqueous environment: A computational study of alkyls on Cu(111). The Journal of Chemical Physics, 145(7). https://doi.org/10.1063/1.4961027

Hydrocarbon adsorption in an aqueous environment: A computational study of alkyls on Cu(111)

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