Solid-State Energetics and Electrostatics: Madelung Constants and Madelung Energies. Leslie Glasser*
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1 Supplementary Tables Solid-State Energetics and Electrostatics: Madelung Constants and Madelung Energies Leslie Glasser* Nanochemistry Research Institute, Department of Chemistry Curtin University, GPO Box U1987, Perth, WA 6845, Australia
2 Values in italics in the Tables below (for CdI 2, BiI 3, VF 3, and Cr 2 O 3 ) have been recalculated using the program GULP (Gale, J. D. J. Chem. Soc., Faraday Trans. 1997, 93). Table S1: Collated crystal structural information on some ionic solids, and related Madelung constant data. Ionic Solid Space Group V m Z M r r o M r /r M a a M a /a M v M v /v 1/3 / nm 3 / nm / nm -1 / nm / nm -1 / nm -1 NaCl C CsCl C TlF O TlI O BaBr 2 O BaI 2 O BaF 2 C BaCl 2 (CaF 2 - type) C BaCl 2 (PbCl 2 - type) O BeCl 2 O CaF 2 (fluorite) C CaCl 2 O CaBr 2 O CaI 2 H CdCl 2 R CdI 2 H CrCl 2 O
3 CuF 2 M HgI 2 T MgF 2 T MgCl 2 H MgBr 2 H MgI 2 H PbCl 2 O PbFCl T SrF 2 C SrCl 2 C SrBr 2 T SrI 2 O TiCl 2 H AlCI 3 M AsI 3 R BiF 3 C BiI 3 R FeCl 3 R IrF 3 R LaCl 3 H LaF 3 H MoF 3 R PuBr 3 O ScF 3 C UD 3 C VF 3 R VI 3 R YF 3 C YCl 3 M AgO C SG? 31.41
4 BaO C BeO H CaO C CdO C CeO C CoO C CuO M CuO M CuO M EuO C FeO C LaO C MgO C NbO C NbO C NdO C NiO C PrO C SnO O SrO C TiO C VO C ZnO H ZnS (sphalerite cubic) C ZnS (wurtzite hexagonal) H α-al 2 O 3 (corundum) R Ce 2 O 3 H Ce 2 O 2 S H Cr 2 O 3 R Cr 2 O 3 H Eu 2 O 3 H Fe 2 O 3 - alpha R
5 Ga 2 O 3 - beta M In 2 O 3 (corundum) R In 2 O 3 (cubic) C La 2 O 3 H LaAlO 3 R Mn 2 O - 3 beta O Nd 2 O 3 H Pb 2 O 3 M Rh 2 O 3 R Sc 2 O 3 C Ti 2 O 3 R V 2 O 3 R V 2 O 3 R Y 2 O 3 H Yb 2 O 3 C MgAl 2 O 4 C CeO 2 C CrO 2 T GeO 2 (rutile) T MnO 2 -beta T MoO 2 M NbO 2 T PbO 2 O PrO 2 C RhO 2 T RuO 2 T SiO 2 T SiO 2 - beta H SnO 2 T TeO 2 T
6 TiO 2 (anatase) T TiO 2 (brookite) O TiO 2 (rutile) T VO 2 T VO 2 O ZrO 2 T ZrO 2 M ZrO 2 C ZrS 2 H ReO 3 C WO 3 T BaBiO 3 C BaTiO 3 C NaTaO 3 C SrTiO 3 C FeOCl O LaOCl T LaOF - beta R LaOF - gamma T YOF R YOCI CuFeO 2 R CuFeO 2 H LiCrO 2 R NaFeO 2 R BaLiF 3 C KZnF 3 C
7 BiOBr T BiSCl O Cu 2 O C Hg 2 Cl 2 T NiAs H SbSI SiF V 2 O 5 O Complex Oxides a LaCoO 3 R LaCrO 3 R LaCuO 3 R LaFeO 3 C LaMnO 3 R LaNiO 3 R LaRhO 3 C LaRuO 3 C LaTiO 3 C LaVO 3 C LaYbO 3 SrCeO 3 C SrCoO 3 C SrCrO 3 C SrMnO 3 C SrMoO 3 C SrSnO 3 C SrTiO 3 C SrVO 3 C
8 La 2 CoO 4 O La 2 CuO 4 O La 2 NiO 4 T LaSrCoO 4 T LaSrCrO 4 T LaSrCuO 4 T LaSrFeO 4 T LaSrNiO 4 T Sr 2 MnO 4 T Sr 2 MoO 4 T Sr 2 RuO 4 T Sr 2 SnO 4 T Sr 2 TiO 4 T Sr 2 VO 4 T a The data for this set of complex oxides has been extracted from Torrance, J. B,Lacorre, P., Asavaroengchai, C., and Metzger, R. M. Physica C, 1991,182,
9 Table S2: Lattice and Madelung (electrostatic) Energies (in kj mol -1 ) for materials treated as ionic. Ionic Solid U POT (BHF) Madelung energy Mr/r Ma/a Mv/v 1/3 NaCl CsCl TlF TlI BaBr BaI BaF BaCl 2 (CaF 2 - type) BaCl 2 (PbCl 2 - type) 2201 BeCl CaF 2 (fluorite) CaCl CaBr CaI CdCl CdI CrCl CuF HgI MgF MgCl
10 MgBr MgI PbCl PbFCl SrF SrCl SrBr SrI TiCl AlCI AsI BiF BiI FeCl IrF LaCl LaF MoF PuBr ScF UD VF VI YF YCl AgO BaO BeO CaO
11 CdO 3806 CeO 3813 CoO CuO CuO CuO EuO 3780 FeO LaO 3780 MgO 3791 NbO NbO NdO 3891 NiO PrO 3858 SnO SrO TiO VO ZnO ZnS (sphalerite cubic) ZnS (wurtzite hexagonal) α-al 2 O 3 (corundum) Ce 2 O Ce 2 O 2 S Cr 2 O Cr 2 O Eu 2 O Fe 2 O 3 - alpha Ga 2 O 3 - beta In 2 O 3 (corundum)
12 In 2 O 3 (cubic) La 2 O LaAlO 3 Mn 2 O 3 - beta Nd 2 O Pb 2 O Rh 2 O Sc 2 O Ti 2 O V 2 O V 2 O Y 2 O Yb 2 O MgAl 2 O CeO CrO GeO 2 (rutile) MnO 2 -beta MoO NbO PbO PrO RhO RuO SiO SiO 2 - beta SnO TeO TiO 2 (anatase) TiO 2 (brookite)
13 TiO 2 (rutile) VO VO ZrO ZrO ZrO ZrS ReO WO BaBiO BaTiO NaTaO SrTiO FeOCl 5432 LaOCl LaOF - beta LaOF - gamma YOF YOCI 6641 CuFeO CuFeO LiCrO NaFeO BaLiF 3 KZnF 3 BiOBr 6432
14 BiSCl 5302 Cu 2 O Hg 2 Cl NiAs SbSI 5208 SiF V 2 O Complex Oxides a LaCoO LaCrO LaCuO LaFeO LaMnO LaNiO LaRhO LaRuO LaTiO LaVO LaYbO 3 SrCeO SrCoO SrCrO SrMnO SrMoO SrSnO SrTiO SrVO La 2 CoO
15 La 2 CuO La 2 NiO LaSrCoO LaSrCrO LaSrCuO LaSrFeO LaSrNiO Sr 2 MnO Sr 2 MoO Sr 2 RuO Sr 2 SnO Sr 2 TiO Sr 2 VO a The data for this set of complex oxides has been extracted from Torrance, J. B,Lacorre, P., Asavaroengchai, C., and Metzger, R. M. Physica C, 1991,182,
16 Table S3: Lattice and Madelung (electrostatic) Energies (in kj mol -1 ) for partially-covalent materials with assumed integer charges. Material UPOT a b E M CuH AuCl AuBr AuI c LiH NaH KH RbH CsH a UPOT = Uvs(calc) IDE from Glasser, L.; von Szentpály, L. Born-Haber-Fajans Cycle Generalized: Linear Energy Relation between Molecules, Crystals and Metals, J. Am. Chem. Soc., 2006, 128, b The values for EM have been calculated using the program GULP (Gale, J. D. J. Chem. Soc., Faraday Trans. 1997, 93), assuming integer charges. c UPOT(AuI) has been estimated using the correlation in Fig. 2 of the main text.
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