Title :

Ab initio interpretation of sum frequency generation spectra of 4-cyanopyridine adsorbed on Au(1 1 1)

Author(s) :

Tadjeddine, M. [Auteur]
Laboratoire des mécanismes réactionnels [DCMR]
Flament, J.P. [Auteur]
Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 [PhLAM]

Journal title :

Chemical Physics

Pages :

27-46

Publisher :

Elsevier

Publication date :

2001

ISSN :

0301-0104

English abstract : [en]

The sum frequency generation spectroscopy allows the in situ vibrational study of 4-cyanopyridine (4-CP) adsorbed on a gold electrode. Our (DFT, MP2, MP2 + SQM) calculations permit to propose: (1) the whole vibrational ...
Show more >The sum frequency generation spectroscopy allows the in situ vibrational study of 4-cyanopyridine (4-CP) adsorbed on a gold electrode. Our (DFT, MP2, MP2 + SQM) calculations permit to propose: (1) the whole vibrational structure of the 4-CP (vibrational frequencies, infrared and Raman intensities) and (2) the interpretation of the adsorption phenomenon. The Au(1 1 1) surface has been modelled by a cluster composed of 28 Au atoms. Our results show that the most stable adsorption configuration is the vertical one when the 4-CP is linking on-top (s axial bond, via N of the pyridine ring). Moreover, the introduction of the electric field in the calculations confirms the observation of the spectra obtained by electrochemical potential scanning: (i) At negative values, the 4-CP is in its stable adsorption geometry; (ii) then, it turns over to a flat configuration (p bond); (iii) at large positive values of the potential, the 4-CP is still vertically linked (s axial bond via N of the cyano group). © 2001 Elsevier Science B.V.Show less >

Language :

Anglais

Peer reviewed article :

Oui

Audience :

Internationale

Popular science :

Non

Collections :

• Laboratoire de Physique des Lasers, Atomes et Molécules (PhLAM) - UMR 8523

Source :

Harvested from HAL