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

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

Montemore, Matthew M.
•
Andreussi, Oliviero  
•
Medlin, J. Will
2016
Journal Of Chemical Physics

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. Published by AIP Publishing.

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Type
research article
DOI
10.1063/1.4961027
Web of Science ID

WOS:000381680700039

Author(s)
Montemore, Matthew M.
Andreussi, Oliviero  
Medlin, J. Will
Date Issued

2016

Publisher

American Institute of Physics

Published in
Journal Of Chemical Physics
Volume

145

Issue

7

Article Number

074702

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
THEOS  
Available on Infoscience
October 18, 2016
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/130317
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