Vibrational spectrum of methoxy adsorbed on metal surfaces: ab initio calculations and experiments

被引：19

作者：

Uvdal, P

MacKerell, AD ^{[1
]}

机构：

[1] Univ Maryland, Sch Pharm, Dept Pharmaceut Sci, Baltimore, MD 21201 USA

[2] Univ Lund, Dept Chem, S-22100 Lund, Sweden

来源：

SURFACE SCIENCE | 1997年 / 393卷 / 1-3期

关键词：

ab initio quantum chemical methods; alcohols; electron energy loss spectroscopy; infrared absorption spectroscopy; molybdenum; photon absorption spectroscopy; rhodium; single crystal surfaces; surface structure; morphology; roughness; and topography;

D O I：

10.1016/S0039-6028(97)00579-7

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Ab initio electronic structure calculations are used to assign the vibrational spectra of methoxy adsorbed on Mo(110). Methoxy with two different orientations with respect to the surface, perpendicular (C-3v) and tilted (C-s), were investigated. Using calculations on Mo-methoxy and Rh-methoxy complexes to represent different orientations and symmetries, it is shown that experimentally observed changes in spectra associated with reorientation and isotopic substitution (CH3O-, CHD2O- and CD3O-) are reproduced completely by the calculations. Problems with the use of vibrational data on gas-phase species for interpreting surface data are presented. Limitations in the approach associated with Fermi resonances are discussed. (C) 1997 Elsevier Science B.V.

引用

页码：141 / 149

页数：9

共 27 条

[21] SURFACE-INDUCED ALTERATION OF ADSORBATE ELECTRONIC-STRUCTURE AND INTRAMOLECULAR VIBRATIONAL COUPLING - THE VIBRATIONAL-SPECTRUM OF 2-PROPOXIDE ON MO(110) AS DETERMINED BY AB-INITIO CALCULATIONS AND EXPERIMENTS [J].