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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 96 (1992), S. 9212-9220 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Low energy helium diffraction has been used to determine the unit mesh parameters of overlayers of CH3Br physisorbed on C(0001), NaCl(001), and LiF(001) at ≈35 K. CH3Br forms a uniaxially commensurate overlayer on C(0001) with unit mesh parameters 4.26 A(ring)×6.75 A(ring). On NaCl(001), CH3Br forms a high coverage and a low coverage phase. The high coverage phase is incommensurate and has unit mesh parameters 4.54 A(ring)×6.73 A(ring), whereas the low coverage phase is commensurate with a ((2)1/2×3(2)1/2)R45° unit mesh. The structure of CH3Br/LiF(001) is essentially the same as that of the high coverage phase of CH3Br/NaCl(001) with unit mesh parameters 4.52 A(ring)×6.71 A(ring). The unit mesh parameters (with the exception of low coverage CH3Br/NaCl ) are very similar to the lattice parameters of the a-b [or (001)] plane of bulk crystalline CH3Br at ≈153 K. By analogy with the bulk crystal, it is likely that there are two molecules per unit mesh and that the CH3Br dipoles are nearly perpendicular to the surface and antiferroelectrically ordered. Our results suggest that the unit mesh for the low coverage phase of CH3Br/NaCl contains four molecules and that the molecular axes are parallel to the substrate surface. The implications of these results for photodissociation studies of physisorbed CH3Br are briefly discussed.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 94 (1991), S. 8493-8502 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Low energy helium diffraction has been used to study the packing and thermal motion of the terminal CH3 groups of monolayers of n-alkane thiols self-assembled on Au(111)/mica films and a Au(111) single crystal surface. At low temperatures (〈100 K), the terminal CH3 groups are arranged in domains containing a hexagonal lattice with a lattice constant of 5.01 A(ring). As the length of the carbon chain is shortened, an abrupt decrease in the diffraction peak intensities is observed for CH3(CH2)9SH/Au(111)/mica, and no diffraction is observed for CH3(CH2)5SH/Au(111)/mica. This is indicative of a sudden decrease in surface order at around ten carbon atoms per chain. A semi-quantitative estimation of the average domain size of each monolayer surface shows a maximum of 46 A(ring) at intermediate chain length [CH3(CH2)13SH/Au(111)/mica], decreasing to 26 A(ring) at longer [CH3(CH2)21SH/Au(111)/mica] and 41 A(ring) at shorter [CH3(CH2)9SH/Au(111)/mica] chain lengths. No phase transitions could be detected at the surfaces of these monolayers from 35 K to 100 K, but as expected for a soft material, the thermal motion of the n-alkane thiol molecules increases with increasing surface temperature and reduces the diffraction intensities to zero at around 100 K. The relative mean square displacements of the surface CH3 groups along the directions perpendicular and parallel to the surface have been calculated from the temperature dependence of the diffraction peak intensities using the standard Debye–Waller formalism. The measured values are in good agreement with the results from a recent molecular dynamics simulation. [J. Hautman and M. Klein, J. Chem. Phys. 93, 7483 (1990).]
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 98 (1993), S. 3503-3511 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We report direct evidence of a unit mesh containing more than one hydrocarbon chain at the surface of a self-assembled monolayer of long-chain n-alkanethiols. Our helium diffraction measurements for a monolayer of n-octadecanethiol on Au(111) are consistent with a rectangular primitive unit mesh of dimensions 8.68×10.02 A(ring) containing four crystallographically distinct hydrocarbon chains. This packing arrangement can also be described as a c(4×2) superlattice with respect to the fundamental simple hexagonal [((square root of)3×(square root of)3)R30°] array of lattice parameter 5.01 A(ring) previously observed for monolayers of other n-alkanethiols on gold. No temperature-dependent phase behavior is observed in the temperature range where surface diffraction is measurable (30–100 K) and cycling up to temperatures as high as 50 °C caused no observable change in the diffraction. It is proposed that this larger unit mesh is the result of a patterned arrangement of rotations of the hydrocarbon chains about their molecular axes. This patterned arrangement must be different than the herringbone structure expected by simple analogy to bulk n-alkanes.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Low-energy helium diffraction has been used to study the surface structure, chain packing, and thermal vibrations of docosyl mercaptan [CH3(CH2)21SH] self-assembled on single crystal Au(111), (110), and (100). The docosyl mercaptan molecules form monolayers with different periodicity on the different surfaces of gold. On Au(111) at low temperatures (≤100 K), the terminal methyl groups of the docosyl mercaptan molecules form domains of a hexagonal lattice with a unit mesh constant of 5.01±0.02 A(ring). The sulfur head groups are arranged in a commensurate ((square root of)3×(square root of)3)R30° structure and are believed to adsorb on the triple hollow sites of the Au(111) lattice. The unit mesh parameters for CH3(CH2)21S/Au(110) are a=b=4.99±0.08 A(ring) and α=109.5°, suggesting that the chemisorbed sulfur atoms remove the "missing row'' reconstruction of the Au(110) surface and form a commensurate c(2×2) lattice. The adsorption of docosyl mercaptan molecules on a Au(100) surface results in a complicated diffraction pattern. Analysis of the data reveals an oblique unit mesh with a=b=5.97±0.09 A(ring) and α=95°±5° with four kinds of equivalent domains present because of the fourfold symmetry of Au(100). The above results confirm that the sulfur–substrate interaction plays an important role in determining the periodicity and the packing density of the molecules within the monolayers. The estimated average domain size of the terminal methyl groups is 22.8, 38.6, and 23.4 A(ring) for CH3(CH2)21SH self-assembled on Au(111), (110), and (100) faces, respectively. The chain packing and orientation within the unit cell are also discussed in this paper in conjunction with the latest results obtained via other techniques such as reflection IR spectroscopy and low-energy electron diffraction.
    Type of Medium: Electronic Resource
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