10.1021/ja067442g.s001
Hervé Lesnard
Hervé
Lesnard
Marie-Laure Bocquet
Marie-Laure
Bocquet
Nicolás Lorente
Nicolás
Lorente
Dehydrogenation of Aromatic Molecules under a Scanning
Tunneling Microscope: Pathways and Inelastic Spectroscopy
Simulations
American Chemical Society
2007
5H
reaction pathway yields
pyridil
adiabatic barriers show
benzene
dehydrogenation products
scanning tunneling microscope
phenyl
6H
Inelastic Spectroscopy SimulationsWe
STM
pyridine
2007-04-11 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Dehydrogenation_of_Aromatic_Molecules_under_a_Scanning_Tunneling_Microscope_Pathways_and_Inelastic_Spectroscopy_Simulations/3013558
We have performed a theoretical study on the dehydrogenation of benzene and pyridine molecules
on Cu(100) induced by a scanning tunneling microscope (STM). Density functional theory calculations
have been used to characterize benzene, pyridine, and different dehydrogenation products. The adiabatic
pathways for single and double dehydrogenation have been evaluated with the nudge elastic band method.
After identification of the transition states, the analysis of the electronic structure along the reaction pathway
yields interesting information on the electronic process that leads to H-scission. The adiabatic barriers
show that the formation of double dehydrogenated fragments is difficult and probably beyond reach under
the actual experimental conditions. However, nonadiabatic processes cannot be ruled out. Hence, in order
to identify the final dehydrogenation products, the inelastic spectra are simulated and compared with the
experimental ones. We can then assign phenyl (C<sub>6</sub>H<sub>5</sub>) and α-pyridil (α-C<sub>5</sub>H<sub>4</sub>N) as the STM-induced
dehydrogenation products of benzene and pyridine, respectively. Our simulations permit us to understand
why phenyl, pyridine, and α-pyridil present tunneling-active C−H stretch modes in opposition to benzene.