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For the S atom near an a-top site the Pt-S distance was 2.31 Å, whereas for the S atom in a mixed hollow-bridge site the two shorter Pt-S distances were 2.46 and 2.47 Å (see Fig. 4).
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72
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0342586156
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note
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(a) For example, using the DMoL3 program [Refs. 32 and 55(b)] with a localized atomic-orbital basis set (double zeta quality plus polarization functions) and the GGA approximation [Becke-88 for exchange (c) and Perdew-91 for correlation (d)], we found that for the systems in Table I the negative Mulliken charge (e) on the sulfur adatoms was always small in absolute terms (<0.3e). For a given adsorption site the negative charge on sulfur decreased with increasing coverage, and in all cases the Pt-S bond was mostly covalent. This can be expected since the Pauling Electronegativities of Pt and S are not very different (f);
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-
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83
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0343456040
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note
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2 species are bonded to two Pt atoms (almost a-top coordination; see the bottom of Fig. 8) with Pt-S bond distances of 2.33 and 2.30 Å.
-
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84
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0342586149
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note
-
In this case, a sulfur atom is almost on top of a Pt atom (Pt-S bond length= 2.34 Å) and the second sulfur is well above a tin atom (Sn-S bond length= 3.21 Å); see Fig. 8.
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