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Upon adsorption on a Cu surface, the spacer legs of the SL molecule can react to the tendency of the board to be attracted to the surface in different ways. On each side of the axis, because of their mutual repulsion, the two legs must move in steps, but independently of the pair on the other side. Thus, the two spacer groups on each side of the center board can each be tilted in one of two ways out of the right-angled orientation. Hence, on the surface, there are three minimum-energy conformations: two chiral (left- or right-handed) enantiomorphic (mirror-image) forms with C2h symmetry (each with a crossed or staggered conformation of legs on opposite sides of the board) and one achiral form with C2 symmetry (self-mirroring, eclipsed conformation of legs on opposite sides of the board, Based on ESQC calculations,16,33,55 the two different molecular shapes (rectangular and rhomboidal) found in the STM images are in turn related to the two possible geometrical conformations
-
16,33,55 the two different molecular shapes (rectangular and rhomboidal) found in the STM images are in turn related to the two possible geometrical conformations of the molecule on the surface. In one conformation, each pair of legs on the same side of the wire axis are parallel to each other but crossed with respect to the pair on the other side of the axis, giving an STM skewed parallelogram shape for four regions of tunneling "contact" of the spacer groups. This form is chiral, since there are two ways ("left" and "right") to do the skewing. In the other achiral form, with the four legs all parallel to each other, only one rectangular shape for the four lobes is observed in STM images. While there is only one image form (only the "feet" of the molecule are imaged), there are two opposite ways to lean the "tops", so when two adsorbed molecules are adjacent along their axes, there will be a different interaction between them according to whether their "tilts" are parallel or antiparallel.
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55149121366
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We use an ESQC routine based on the calculation of the full scattering matrix of the STM tunnel junction as scans over the whole molecule. The description of this junction encompasses the surface, the adsorbate, the tip apex, and both the bulk material supporting the tip apex and the surface. Whatever the tip apex position, several hundred molecular orbitals are used to describe the electronic properties of the junction with the organic molecule positioned under the tip apex. The surface atoms and the organic molecule are described taking into account all valence molecular orbitals. Electronic interactions inside the junction are calculated using a semiempirical extended Hückel approximation with a double-ζ basis set, in order to properly reproduce the tip apex wave function in space away from the tip apex end atom. The MM2 routine used in conjunction with ESQC to optimize molecular geometries in the tunnel junction is a standard MM2 routine with a generalized potential for s
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We use an ESQC routine based on the calculation of the full scattering matrix of the STM tunnel junction as scans over the whole molecule. The description of this junction encompasses the surface, the adsorbate, the tip apex, and both the bulk material supporting the tip apex and the surface. Whatever the tip apex position, several hundred molecular orbitals are used to describe the electronic properties of the junction with the organic molecule positioned under the tip apex. The surface atoms and the organic molecule are described taking into account all valence molecular orbitals. Electronic interactions inside the junction are calculated using a semiempirical extended Hückel approximation with a double-ζ basis set, in order to properly reproduce the tip apex wave function in space away from the tip apex end atom. The MM2 routine used in conjunction with ESQC to optimize molecular geometries in the tunnel junction is a standard MM2 routine with a generalized potential for surface metal atoms.
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At RT on Cu110, the molecules diffuse rapidly across the surface and are frequently found at step edges, from which we infer that the latter are sites from which diffusion is hindered. This adsorption is accompanied by the formation of Cu nanostructures protruding from the step edge, to which the molecules are effectively anchored. See refs 12 and 25-27
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At RT on Cu(110), the molecules diffuse rapidly across the surface and are frequently found at step edges, from which we infer that the latter are sites from which diffusion is hindered. This adsorption is accompanied by the formation of Cu nanostructures protruding from the step edge, to which the molecules are effectively anchored. See refs 12 and 25-27.
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3Au(100) and 2.9 eV in the case of adsorption on Ag(111), confirming that this measurement is significantly surface dependent, as expected from the fact that SLs adopt different conformations on different substrates (Final Report of the Bottom Up Nanomachines EU Project, 2002).
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3Au(100) and 2.9 eV in the case of adsorption on Ag(111), confirming that this measurement is significantly surface dependent, as expected from the fact that SLs adopt different conformations on different substrates (Final Report of the "Bottom Up Nanomachines" EU Project, 2002).
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