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Title: The interaction of organic adsorbate vibrations with substrate lattice waves in methyl-Si(111)-(1 × 1)

A combined helium atom scattering and density functional perturbation theory study has been performed to elucidate the surface phonon dispersion relations for both the CH{sub 3}-Si(111)-(1 × 1) and CD{sub 3}-Si(111)-(1 × 1) surfaces. The combination of experimental and theoretical methods has allowed characterization of the interactions between the low energy vibrations of the adsorbate and the lattice waves of the underlying substrate, as well as characterization of the interactions between neighboring methyl groups, across the entire wavevector resolved vibrational energy spectrum of each system. The Rayleigh wave was found to hybridize with the surface rocking libration near the surface Brillouin zone edge at both the M{sup ¯}-point and K{sup ¯}-point. The calculations indicated that the range of possible energies for the potential barrier to the methyl rotation about the Si-C axis is sufficient to prevent the free rotation of the methyl groups at a room temperature interface. The density functional perturbation theory calculations revealed several other surface phonons that experienced mode-splitting arising from the mutual interaction of adjacent methyl groups. The theory identified a Lucas pair that exists just below the silicon optical bands. For both the CH{sub 3}- and CD{sub 3}-terminated Si(111) surfaces, the deformations of the methyl groups were examined andmore » compared to previous experimental and theoretical work on the nature of the surface vibrations. The calculations indicated a splitting of the asymmetric deformation of the methyl group near the zone edges due to steric interactions of adjacent methyl groups. The observed shifts in vibrational energies of the -CD{sub 3} groups were consistent with the expected effect of isotopic substitution in this system.« less
Authors:
; ;  [1] ; ;  [2] ; ;  [3] ;  [2] ;  [4]
  1. The James Franck Institute and Department of Chemistry, The University of Chicago, 929 E. 57th Street, Chicago, Illinois 60637 (United States)
  2. Dipartimento di Scienza dei Materiali, Universitá di Milano-Bicocca, Via Cozzi 53, 20125 Milano (Italy)
  3. Beckman Institute and Kavli Nanoscience Institute, Division of Chemistry and Chemical Engineering, 210 Noyes Laboratory, 127-72, California Institute of Technology, Pasadena, California 91125 (United States)
  4. (DIPC), Universidad del País Vasco (EHU), 20018 Donostia / San Sebastian (Spain)
Publication Date:
OSTI Identifier:
22308781
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 141; Journal Issue: 2; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ATOMS; BRILLOUIN ZONES; DENSITY FUNCTIONAL METHOD; DISPERSION RELATIONS; ENERGY SPECTRA; HELIUM; INTERACTIONS; ISOTOPIC EXCHANGE; PHONONS; RAYLEIGH WAVES; ROTATION; SCATTERING; SILICON; SUBSTRATES; SURFACES