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In a halogen bond (R-X-Y-R′), the halide, X, is bonded to some moderately to very electron withdrawing group R. The group electronegativity of R determines how substantial the shift in the electron density along the bond axis - away from X and toward R - will be.
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We use the term "strength" instead of electrophilicity to refer to the positive electrostatic potential (ESP) within the σ-hole. The σ-hole gets stronger as the ESP gets more positive.
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See also refs 5 - 13 therein. As this reference emphasizes, halogen bonding depends on the variation in the charge distribution (hence the magnitude and sign of the electrostatic potential) across the surface of X atoms in molecules. This critical level of detail is sacrificed in point charge models
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Even if X in the acid/base pair R-X-Y-R′ has a noticeable local σ-hole (outside the bonding region; see Figure 1) it is still possible for X to have a net (global) negative charge if, in the bonding region, the R → X charge transfer is significant. Now, since Y is necessarily an electron-rich site, it would have a net negative change as well. Thus, a simple point charge model would predict, incorrectly, that the interaction between X and Y is always repulsive, independent of the R-X-Y bond angle. See ref 32.
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Results obtained at the MP2 level for the halomethanes, and their silicon and germanium analogues have been presented and discussed in detail in parts 1 and 2 of the series. Small differences have been observed between the geometrical and other MP2(full) data from this work for C, Si, and Ge (shown in the supporting information) and the data available in the preceding papers in the series.
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In contrast to the less expensive MP2 method, the MP2(full) method takes all the core electrons into account in assessing the contributions of the doubly excited state to the total energy of the system.
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The relatively smaller changes in the atomic radii after silicon are explained by the well known d-orbital and lanthanide contractions (after period three, and from periods five (Sn) to six (Pb), respectively). For Pb, relativistic effects are responsible for a contraction of the valence s and p orbitals, as well.
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67
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77954331453
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