Outstanding Energy Exchange between Organic Molecules and Metal Surfaces: Decomposition Kinetics of Excited Vinyl Derivatives Driven by the Interaction with a Cu(111) Surface
Entity
UAM. Departamento de QuímicaPublisher
American Chemical SocietyDate
2019-08-15Citation
10.1021/acs.jpcc.9b04898
Journal of Physical Chemistry C 123.32 (2019): 19625-19636
ISSN
1932-7455 (online); 1932-7447 (print)DOI
10.1021/acs.jpcc.9b04898Funded by
This work was partially supported by the project CTQ2016-76061-P of the Spanish Ministerio de Economía 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 “María 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.9b04898Subjects
Density functional theory; Dispersion correction; Functionals; Amides; Chemisorption; Descomposition; Energy dissipation; Molecular dynamics; Molecular orientation; Molecules; Van der Waals forces; QuímicaNote
This document is the Accepted Manuscript version of a Published Work that appeared in final form in 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.9b04898Rights
© 2019 American Chemical SocietyAbstract
Here, we present a thorough theoretical study of the interaction, chemisorption, and thermal decomposition of three vinyl derivatives (acrolein, acrylonitrile, and acrylamide) on a pristine Cu(111) surface. To this, we have carried out density functional theory simulations, including weak van der Waals forces, in the framework of periodic boundary conditions. The results have shown strong anchoring between the molecules and the surface through the vinyl group, with the different functional groups driving molecular orientation. We explain the chemisorption with a simple chemical picture: donation from the occupied lone pair and πorbitals of the molecule to the surface and backdonation from the surface to the π∗ orbital of the molecule (π-backbonding). Ab initio molecular dynamics simulations highlight the efficient energy exchange in excited adsorbed molecules and energy dissipation through the interface, which takes place in a few hundreds of femtoseconds. The study of the dynamics also allows to comprehend the catalytic effect of the chemisorption, which is reflected not only in the larger amount of fragmentation but also in the much richer spectrum of fragments observed with respect to the molecular decomposition in the gas phase
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Google Scholar:Aguilar-Galindo Rodríguez, Fernando
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Díaz-Tendero Victoria, Sergio
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