A simple and accurate approach for calculating the vibration spectra of molecules on surfaces: Comparisons to high resolution electron energy loss data for ethylene on silicon

Peak assignment is a complex but important task for analyzing the vibration spectra of surface-bound molecules. Here we describe a simple approach for calculating infrared and Raman spectra for surface-bound molecules using a cluster model approach with quantum capping potentials (QCPs). The utility of the approach is demonstrated by comparisons to the measured high resolution electron energy loss spectra for ethylene on clean silicon. By capping the silicon cluster with QCPs we computed spectra that agree very well with the HREEL spectrum, allowing us to easily assign the experimental peaks. QCPs are similar to effective core potentials, can be used with any ab initio technique and most computational chemistry packages, and their use requires no special expertise. (c) 2006 Elsevier B.V. All rights reserved.