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The clean Si (100) -2x1 surface has rows of dimers of Si atom that share in a strong σ-bond and a weak π-bond. The distance between dimers in a row is ∼3.85 Å, and the periodicity of the rows is ∼7.70 Å. We refer to the space between dimer rows as a gulley.
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The clean Si (100) -2x1 surface has rows of dimers of Si atom that share in a strong σ-bond and a weak π-bond. The distance between dimers in a row is ∼3.85 Å, and the periodicity of the rows is ∼7.70 Å. We refer to the space between dimer rows as a "gulley".
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The structure of hydrogen-terminated Si (100) -2 × 1 is similar to that of the clean surface, 2 except that the weak π-bond shared by dimer row Si atoms is replaced by σ-bonds to capping hydrogen atoms.
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The structure of hydrogen-terminated Si (100) -2 × 1 is similar to that of the clean surface, 2 except that the weak π-bond shared by dimer row Si atoms is replaced by σ-bonds to capping hydrogen atoms.
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In ref 18, we optimized silicon DCPs for use with B971 26/6-31+G (d, p) and with carbon DCPs. For the present work, we reoptimized the Si DCP coefficients for use with PBE/6-31+G (d, p) following the approach we used in ref 18. The PBE method, as implemented in ref 17, is computationally more efficient, in terms of computational speed, than B971. The optimized coefficients for silicon are c1, 0.00053 and c 2= 0.00165. These coefficients were determined by minimizing the mean absolute deviations (MAD) of PBE/6-31+G (d, p, DCP binding energies relative to high-level wave function data for six conformations each of the methane-silane and silane-benzene dimers. The high-level data were obtained by complete basis set extrapolated CCSD (T) calculations, which generally provide fairly accurate estimates of dispersion binding energies. The MADs of the BEs determined using PBE/6-31 +G (d, p) with the optimized DCPs are 0.14 kcal/mol for methane-silane a
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2= 0.00165. These coefficients were determined by minimizing the mean absolute deviations (MAD) of PBE/6-31+G (d, p) -DCP binding energies relative to high-level wave function data for six conformations each of the methane-silane and silane-benzene dimers. The high-level data were obtained by complete basis set extrapolated CCSD (T) calculations, which generally provide fairly accurate estimates of dispersion binding energies. The MADs of the BEs determined using PBE/6-31 +G (d, p) with the optimized DCPs are 0.14 kcal/mol for methane-silane and 0.06 kcal/mol for silane-benzene. As a check, we calculated the BEs of benzene on the model H-Si (100) - (2x1) that we used in ref 18. For four configurations of benzene on H-Si (100) - (2x1), PBE/6-31+G (d, p) -DCP predicted BEs that are 0.2-0.3 kcal/mol (4.3-5.2%) lower than the B971/6-31+G (d, p) -DCP values. This minor difference in calculated BEs was deemed to be a worthwhile tradeoff for the high speed of PBE over B971. Additional details are provided in the Supporting Information.
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67649992653
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Our calculated data, plotted in Figure S2 of the Supporting Information, indicate that polyacene binding to H-Si 100, 2x1 increases monotonically as a function of the number of rings in the molecule
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Our calculated data, plotted in Figure S2 of the Supporting Information, indicate that polyacene binding to H-Si (100) -2x1 increases monotonically as a function of the number of rings in the molecule.
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84869368135
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One Reviewer correctly pointed out that previous experimental work showed that tetracene molecules in monolayers interact with the surface in an edge-on fashion rather than lying flat on the surface as in Figure 1a.30 We calculated that such an interaction involving a long edge of a single pentacene results in 6.8 kcal/mol of dispersion binding. However, such an edge-on arrangement allows pentacene molecules to π-stack with each other, which is favorable by ∼15.6 kcal/mol according to our calculations. Taking into account that a molecule laying flat on the surface occupies more surface area than does an edge-on molecule, it is clear that in the limit of full monolayer coverage, the edge-on orientation is preferred
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One Reviewer correctly pointed out that previous experimental work showed that tetracene molecules in monolayers interact with the surface in an "edge-on" fashion rather than lying flat on the surface as in Figure 1a.30 We calculated that such an interaction involving a long edge of a single pentacene results in 6.8 kcal/mol of dispersion binding. However, such an edge-on arrangement allows pentacene molecules to π-stack with each other, which is favorable by ∼15.6 kcal/mol according to our calculations. Taking into account that a molecule laying flat on the surface occupies more surface area than does an edge-on molecule, it is clear that in the limit of full monolayer coverage, the edge-on orientation is preferred.
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33751186918
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See, for example
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See, for example: Tersigni, A.; Shi, J.; Jiang, D. T.; Qin, X. R. Phys. Rev. B 2006, 74, 205326.
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It is most likely that the potential energy curve associated with the rotation of pentacene on the surface does not smoothly increase from the row-aligned structure to this transition-state-like structure. More likely, the energy curve displays a number of shallow minima over the range of rotation angles defined by these two structures
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It is most likely that the potential energy curve associated with the rotation of pentacene on the surface does not smoothly increase from the row-aligned structure to this transition-state-like structure. More likely, the energy curve displays a number of shallow minima over the range of rotation angles defined by these two structures.
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67649970838
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The prime is used to denote an energetically equivalent structure to that shown in Figure 1a.
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The prime is used to denote an energetically equivalent structure to that shown in Figure 1a.
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84869338852
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We performed some additional calculations to explore diffusion along the row direction for pentacene bound on one edge of a dimer row. For these calculations, the structure shown in Figure 1a was translated along the dimer row in increments representing 1/10 of the dimer-dimer separation calculated to be 3.86 Å, These calculations indicate that the barrier height for diffusion along the dimer row is 1.8 kcal/mol
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We performed some additional calculations to explore diffusion along the row direction for pentacene bound on one edge of a dimer row. For these calculations, the structure shown in Figure 1a was translated along the dimer row in increments representing 1/10 of the dimer-dimer separation (calculated to be 3.86 Å). These calculations indicate that the barrier height for diffusion along the dimer row is 1.8 kcal/mol.
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Similar calculations were performed in ref 18
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Similar calculations were performed in ref 18.
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Using a very large surface consisting of 7 rows of 11 dimers each and 16 silicon layers, the dispersion energy increases to 23.6 kcal/mol. This means that the silicon surface model that we used for our calculations recovers all but ∼100 × (23.6-21.4) /23.6) 9.3% of the dispersion energy
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Using a very large surface consisting of 7 rows of 11 dimers each and 16 silicon layers, the dispersion energy increases to 23.6 kcal/mol. This means that the silicon surface model that we used for our calculations recovers all but ∼100 × (23.6-21.4) /23.6) 9.3% of the dispersion energy.
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On the basis of a simple Arrhenius expression and using T= 5 K, the temperature at which the STM experiments were performed in ref 18.
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On the basis of a simple Arrhenius expression and using T= 5 K, the temperature at which the STM experiments were performed in ref 18.
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