SEMIEMPIRICAL CALCULATIONS OF THE VIBRATIONAL FREQUENCY OF CARBON-MONOXIDE ADSORBED ON NOBLE-METAL SINGLE-CRYSTAL SURFACES

Citation
Pap. Olivera et al., SEMIEMPIRICAL CALCULATIONS OF THE VIBRATIONAL FREQUENCY OF CARBON-MONOXIDE ADSORBED ON NOBLE-METAL SINGLE-CRYSTAL SURFACES, Journal of electroanalytical chemistry [1992], 351(1-2), 1993, pp. 65-79
Citations number
31
Categorie Soggetti
Electrochemistry,"Chemistry Analytical
Journal title
Journal of electroanalytical chemistry [1992]
ISSN journal
15726657 → ACNP
Volume
351
Issue
1-2
Year of publication
1993
Pages
65 - 79
Database
ISI
SICI code
Abstract
In this work we perform a theoretical analysis of the shift of the obs erved IR reflection-absorption spectroscopy (IRRAS) band of CO adsorbe d on Pt(111), Rh(111) and Pt(100) single crystals as a function of bot h the degree of CO surface coverage and the electric potential applied at either the metal-vacuum or the metal-solution interface. The wavef unctions obtained using a modified extended Huckel molecular orbital ( EHMO) method are used to predict the vibrational frequency data. The P t(110), Rh(111) and Pt(111) single crystals are modelled by bilayer cl usters of 25 and 22 atoms respectively. A theoretical description of t he observed IRRAS shift is analysed by means of a population analysis of CO molecular orbitals, which confirms the donation-back-donation mo del.