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The attempt to achieve the densest possible pattern based on five-fold symmetry is a classic puzzle. After Dürer's motifs (Figure 2 c, top inset; cf. Dürer, A., 1st ed.; Hieronymus Formschneyder, Nürenberg, 1525), Kepler investigated mixed patterns such as the "Aa" tiling in Figure 2 c (bottom inset), which includes one of the first reported "decagon of edge-sharing pentagons" motifs (cf. Kepler, J. Harmonices Mundi Libri V Francof., 1619). Interestingly, this structure (Figure 2 a) is the largest regular polygon that can be built from edge-sharing equal regular polygons.
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The attempt to achieve the densest possible pattern based on five-fold symmetry is a classic puzzle. After Dürer's motifs (Figure 2 c, top inset; cf. Dürer, A. Unterweysung der Messung, 1st ed.; Hieronymus Formschneyder, Nürenberg, 1525), Kepler investigated mixed patterns such as the "Aa" tiling in Figure 2 c (bottom inset), which includes one of the first reported "decagon of edge-sharing pentagons" motifs (cf. Kepler, J. Harmonices Mundi Libri V Francof., 1619). Interestingly, this structure (Figure 2 a) is the largest regular polygon that can be built from edge-sharing equal regular polygons.
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The charge transfer was computed by integrating the total electron density in two separate regions, divided by a x y plane located midway in between the Au surface and the molecule. Note that the electronic wavefunction corresponding to the HOMO peak in the top panel of Figure 3 b is purely rubrene-like; that is, it does not mix with the Au states (hybridization effects are negligible in this system). The partial hole on rubrene then follows from the fractional population of the HOMO state, according to the Fermi-Dirac distribution used in the calculation.
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The charge transfer was computed by integrating the total electron density in two separate regions, divided by a x y plane located midway in between the Au surface and the molecule. Note that the electronic wavefunction corresponding to the HOMO peak in the top panel of Figure 3 b is purely rubrene-like; that is, it does not mix with the Au states (hybridization effects are negligible in this system). The partial hole on rubrene then follows from the fractional population of the HOMO state, according to the Fermi-Dirac distribution used in the calculation.
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The contribution of the molecular internal screening response is expected to be strongest for the case of highly polarizable phenyl groups or aromatic backbones oriented perpendicular to the surface. Such correction was estimated to about 0.2 eV in the case of upright benzene on graphite. (13) Rubrene has a more complicated geometry, with its subunits oriented at various angles to the metallic surface, but at the same time is overall more polarizable than benzene; we expect the correction to be of the same order of magnitude.
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The contribution of the molecular internal screening response is expected to be strongest for the case of highly polarizable phenyl groups or aromatic backbones oriented perpendicular to the surface. Such correction was estimated to about 0.2 eV in the case of upright benzene on graphite. (13) Rubrene has a more complicated geometry, with its subunits oriented at various angles to the metallic surface, but at the same time is overall more polarizable than benzene; we expect the correction to be of the same order of magnitude.
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78650736189
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In rubrene molecular crystals the IP is ∼1.1 eV lower than in gas phase, due to hole polarization screening. In smaller assemblies, though, each molecule has fewer neighbors (only two in a pentagon); therefore, the effect is expected to be less pronounced and minor with respect to the other contributions.
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In rubrene molecular crystals the IP is ∼1.1 eV lower than in gas phase, due to hole polarization screening. In smaller assemblies, though, each molecule has fewer neighbors (only two in a pentagon); therefore, the effect is expected to be less pronounced and minor with respect to the other contributions.
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Conversely, these observations are incompatible with an induced density of states (IDIS) in the molecular gap due to molecule-substrate hybridization effects, as this would imply fractional charging for all molecules, and a smaller energy shift than the "Shockley Mott" 0.8 eV value. (31) Thus, of the two main models currently used to investigate level alignment in organic/metal interfaces, the rubrene/Au(111) system is better described by the ICT model (31) than by the IDIS model (Vazquez, H. et al.,-112). This is consistent with the low degree of mixing of the rubrene π-electronic wavefunctions with the substrate states, due to the non-flat adsorption geometry. For a discussion of dynamical screening for weak molecule-metal couplings, see Thygesen arXiv:0810.5214v1 [cond-mat.mtrl-sci].
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Conversely, these observations are incompatible with an induced density of states (IDIS) in the molecular gap due to molecule-substrate hybridization effects, as this would imply fractional charging for all molecules, and a smaller energy shift than the "Shockley Mott" 0.8 eV value. (31) Thus, of the two main models currently used to investigate level alignment in organic/metal interfaces, the rubrene/Au(111) system is better described by the ICT model (31) than by the IDIS model (Vazquez, H. et al. Appl. Surf. Sci. 2004, 234, 107-112). This is consistent with the low degree of mixing of the rubrene π-electronic wavefunctions with the substrate states, due to the non-flat adsorption geometry. For a discussion of dynamical screening for weak molecule-metal couplings, see Thygesen arXiv:0810.5214v1 [cond-mat.mtrl-sci].
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