Dispersion corrected Density Functional Theory calculations were employed to study the adsorption of benzenes derivatized with functional groups encompassing a large region of the activated/deactivated spectrum to the Ag(111) surface. Benzenes substituted with weak activating or deactivating groups, such as methyl and fluoro, do not have a strong preference for adsorbing to a particular site on the substrate, with the corrugations in the potential energy surface being similar to those of benzene. Strong activating (N(CH3)2) and deactivating (NO2) groups, on the other hand, possess a distinct site preference. The nitrogen in the former prefers to lie above a silver atom (top site), but in the latter a hollow hexagonal-closed-packed (Hhcp) site of the Ag(111) surface is favored instead. Benzenes derivatized with classic activating groups donate electron density from their highest occupied molecular orbital to the surface, and those functionalized with deactivating groups withdraw electron density from the surface into orbitals that are unoccupied in the gas phase. For benzenes functionalized with two substituents, the groups that are strongly activating or deactivating control the site preference and the other groups assume sites that are, to a large degree, dictated by their positions on the benzene ring. The relative stabilities of the ortho, meta, and para positional isomers of disubstituted benzenes can, in some cases, be modified by adsorption to the surface.
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14 March 2015
Research Article|
February 24 2015
Benzene derivatives adsorbed to the Ag(111) surface: Binding sites and electronic structure
Daniel P. Miller
;
Daniel P. Miller
1Department of Chemistry,
State University of New York at Buffalo
, Buffalo, New York 14260-3000, USA
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Scott Simpson;
Scott Simpson
1Department of Chemistry,
State University of New York at Buffalo
, Buffalo, New York 14260-3000, USA
2
School of Science, Penn State Erie, The Behrend College
, 4205 College Drive, Erie, Pennsylvania 16563, USA
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Nina Tymińska;
Nina Tymińska
1Department of Chemistry,
State University of New York at Buffalo
, Buffalo, New York 14260-3000, USA
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Daniel P. Miller
1
Scott Simpson
1,2
Nina Tymińska
1
Eva Zurek
1,a)
1Department of Chemistry,
State University of New York at Buffalo
, Buffalo, New York 14260-3000, USA
2
School of Science, Penn State Erie, The Behrend College
, 4205 College Drive, Erie, Pennsylvania 16563, USA
a)
Electronic mail: [email protected]
J. Chem. Phys. 142, 101924 (2015)
Article history
Received:
November 30 2014
Accepted:
February 04 2015
Citation
Daniel P. Miller, Scott Simpson, Nina Tymińska, Eva Zurek; Benzene derivatives adsorbed to the Ag(111) surface: Binding sites and electronic structure. J. Chem. Phys. 14 March 2015; 142 (10): 101924. https://doi.org/10.1063/1.4908267
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