The dipole moment derivatives of gaseous benzene: A comparison of experimental and ab initio values

Keefe, C. Dale

doi:10.1016/j.chemphys.2006.04.005

Cited by 3 publications

(1 citation statement)

References 61 publications

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“…Furthermore, CCSD(T) and cc-pVXZ basis sets (where X = D, T), or their augmented variants, have been successfully used to optimize the geometries and calculate various properties of benzene and its derivatives. [53][54][55] Since the CCSD(T) and DFT-D2 results were generally in good agreement with one another (see Table IV), and because it would be impossible to carry out CCSD(T) calculations on benzene derivatives adsorbed to Ag(111), the latter less expensive method was applied in this study.…”

Section: Computational Detailsmentioning

confidence: 68%

Benzene derivatives adsorbed to the Ag(111) surface: Binding sites and electronic structure

Miller

Simpson

Tymińska

et al. 2015

The Journal of Chemical Physics

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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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Section: Computational Detailsmentioning

confidence: 68%