Theoretical Insights into Vinyl Derivatives Adsorption on a Cu(100) Surface
Entity
UAM. Departamento de QuímicaPublisher
American Chemical SocietyDate
2018-12-06Citation
10.1021/acs.jpcc.8b06142
Journal of Physical Chemistry C 122.48 (2018): 27301-27313
ISSN
1932-7447 (print); 1932-7455 (online)DOI
10.1021/acs.jpcc.8b06142Funded by
This work was partially supported by the project CTQ2016-76061-P of the Spanish Ministerio de Economı́a y Competitividad (MINECO). F.A.G. acknowledges the FPI grant associated with the project CTQ2013-43698-P (MINECO). Financial support from the MINECO through the “Marı́a de Maeztu” Program for Units of Excellence in R&D (MDM-2014-0377) is also acknowledgedProject
Gobierno de España. CTQ2016-76061-P; Gobierno de España. CTQ2013-43698-P; Gobierno de España. MDM-2014-0377Editor's Version
https://doi.org/10.1021/acs.jpcc.8b06142Subjects
Density functional theory; Adsorption; Aldehydes; Amides; Artificial intelligence; Chemical analysis; Chemical bonds; Herbicides; Molecules; Van der Waals forces; Dispersion correction; Functionals; QuímicaNote
This document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Physical Chemistry C, © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/abs/10.1021/acs.jpcc.8b06142Rights
© 2018 American Chemical SocietyAbstract
Here, we present a thorough theoretical study of the adsorption of acrolein (ACO), acrylonitrile (ACN), and acrylamide (ACA) on Cu(100) surface. For this purpose, we have used the density functional theory, imposing periodic boundary conditions to have a correct description of the electronic band structure of the metal and including dispersion forces through two different schemes: the D2 method of Grimme and the vdW-DF. We have found several adsorption geometries. In all of them, the vinyl group together with the amide (in ACA), ciano (in ACN), and carbonyl (in ACO) groups, is highly involved. The highest adsorption energy is found for acrylamide, followed by acrolein and the lowest for acrylonitrile (depending on the level of theory employed ∼1.2, 1.0, and 0.9 eV, respectively). We show that a strong coupling between the π electronic system (both occupied and virtual orbitals) and the electronic levels of the metal is mainly responsible of the chemisorption. As a consequence, electronic density is transferred from the surface to the molecule, whose carbon atoms acquire a partial sp3 hybridization. Lone-pair orbitals of the cyano, amide, and carbonyl groups also play a role in the interaction. The simulations and following analysis allow to disentangle the nature of the interaction, which can be explained on the basis of a simple chemical picture: donation from the occupied lone pair and π orbitals of the molecule to the surface and backdonation from the surface to the π∗ orbital of the molecule (π-backbonding)
Files in this item
Google Scholar:Aguilar-Galindo Rodríguez, Fernando
-
Díaz-Tendero Victoria, Sergio
This item appears in the following Collection(s)
Related items
Showing items related by title, author, creator and subject.