Cohesive Energies and Enthalpies: Complexities, Confusions, and Corrections

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1 Cohesive Energies and Enthalpies: Supplementary Information Complexities, Confusions, and Corrections Leslie Glasser a, * and Drew Sheppard b a Nanochemistry Research Institute, Department of Chemistry Curtin University, GPO Box U1987, Perth, WA 6845, Australia b Hydrogen Storage Research Group, Fuels and Energy Technology Institute, Department of Physics and Astronomy, Curtin University, GPO Box U1987, Perth, WA 6845, Australia 4 Figures 3 Tables * Corresponding author L. Glasser: Telephone: Fax: l.glasser@curtin.edu.au S1

2 Table S1: Published experimental cohesive energies (column 2) in the energy units listed in column 1, followed by the formation enthalpy of the ionic solid and the enthalpies of the contributing atoms, finally summed in the column headed Sum. This result is to be compared with the cohesive energy converted a to kj mol -1 per formula unit in the penultimate column. 1 The integer factor n corrects from the particular formula unit used in column 2. The final column compares the thermodynamic summation with the published experimental cohesive energy. The data have been sorted into alphabetical order of the chemical formula (column 3). Energy unit ref Cohes. E. Material Δ f H Atom Contributions / kj mol -1 Enthalpy Sum Cohes. E. n n Cohes. E. /kj mol -1 M(g) Δ f H(M,g) X(g) Δ f H(X,g) /kj mol -1 Enthalpy Sum /n Cohes E. ev Al 2 O Al(g) O(g) kcal AlAs Al(g) As(g) kcal AlP Al(g) P(g) kcal AlSb Al(g) Sb(g) kj BaO Ba(g) O(g) ev BaO Ba(g) O(g) kj CaAl Ca(g) Al(g) kj CaO Ca(g) O(g) ev CaO Ca(g) O(g) kcal CdS Cd(g) S(g) kcal CdSe Cd(g) Se(g) S2

3 kcal CdTe Cd(g) Te(g) kj CeAl Ce(g) Al(g) kj CeIr Ce(g) Ir(g) kj CoO Co(g) O(g) ev Cr 2 O Cr(g) O(g) ev CrO Cr(g) O(g) ev Fe 2 O Fe(g) O(g) ev Fe 3 O Fe(g) O(g) kj FeO Fe(g) O(g) ev FeO Fe(g) O(g) ev GaAs Ga(g) As(g) kcal GaAs Ga(g) As(g) kcal 7 76 GaAs Ga(g) As(g) ev GaN Ga(g) N(g) kcal GaP Ga(g) P(g) kcal GaSb Ga(g) Sb(g) kcal 7 69 GaSb Ga(g) Sb(g) kcal InAs In(g) As(g) kcal 7 66 InAs In(g) As(g) S3

4 kcal InP In(g) P(g) kcal 7 77 InP In(g) P(g) kcal InSb In(g) Sb(g) kcal 7 64 InSb In(g) Sb(g) ev K 2 O K(g) O(g) Hartree KCl K(g) 89.0 Cl(g) Hartree KF K(g) 89.0 F(g) kj LaIr La(g) Ir(g) Hartree LiCl Li(g) Cl(g) Hartree LiF Li(g) F(g) kj MgCu Mg(g) Cu(g) kj MgNi Mg(g) Ni(g) kj MgO Mg(g) O(g) ev MgO Mg(g) O(g) kj MgZn Mg(g) Zn(g) kj MnO Mn(g) O(g) ev MoO Mo(g) O(g) Rydberg Na 2 O Na(g) O(g) ev Na 2 O Na(g) O(g) S4

5 Hartree NaCl Na(g) Cl(g) Hartree NaF Na(g) F(g) ev Nb 2 O Nb(g) O(g) kj NbCr 2-7 Nb(g) Cr(g) kj NbFe Nb(g) Fe(g) ev NiO Ni(g) O(g) kj NiO Ni(g) O(g) ev RuO Ru(g) O(g) kj ScCo Sc(g) Co(g) kj ScFe Sc(g) Fe(g) ev SnO Sn(g) O(g) kj SrO Sr(g) O(g) ev SrO Sr(g) O(g) kj TaCr 2-9 Ta(g) Cr(g) ev Ti 2 O Ti(g) O(g) ev TiO Ti(g) O(g) ev TiO Ti(g) O(g) ev TiO Ti(g) O(g) kj UFe U(g) Fe(g) S5

6 ev V 2 O V(g) O(g) ev VO V(g) O(g) kcal ZnS Zn(g) S(g) kcal ZnSe Zn(g) Se(g) kcal ZnTe Zn(g) Te(g) ev ZrO Zr(g) O(g) a Conversion factors applied 1 : 1 hartree = 2 Ry = kj mol -1 ; 1 ev = kj mol -1 ; 1 kcal mol -1 = kj mol -1 S6

7 Table S2: Lattice energies, U pot, derived from tables of incorrectly identified cohesive energies, sorted alphabetically by chemical formula. The U pot values in the penultimate column are from Jenkins and Roobottom. 12 Apparent Cohes. E. Material Apparent Cohes. E. U pot (calc) Upot(calc) /Apparent Cohes. E. /kcal mol -1 /kj mol AlAs AlP AlSb BaO BaS BaSe BaTe CaO CaS CaSe CaTe CdS CdSe CdTe GaAs GaP GaSb InAs InP InSb KBr KCl KF KI LiBr LiCl LiF LiI MgO MgS MgSe NaBr NaCl NaF NaI RbBr RbCl S7

8 186 RbF RbI SrO SrS SrSe SrTe ZnS ZnSe ZnTe S8

9 Table S3: Cohesive energies of alkaline-earth halides calculated via thermodynamic enthalpy summation. 13 Von Szentpaly 14 has a more extensive list for these and related materials. Material f H Atom Contributions / kj mol -1 Moles of /kj mol -1 M(g) f H(M,g) M X(g) f H(X,g) Cohesive Energy Moles of X /kj mol -1 MgF Mg(g) F(g) MgCl Mg(g) Cl(g) MgBr Mg(g) Br(g) MgI Mg(g) I(g) CaF Ca(g) F(g) CaCl Ca(g) Cl(g) CaBr Ca(g) Br(g) CaI Ca(g) I(g) SrF Sr(g) F(g) SrCl Sr(g) Cl(g) SrBr Sr(g) Br(g) SrI Sr(g) I(g) BaF Ba(g) F(g) BaCl Ba(g) Cl(g) BaBr Ba(g) Br(g) BaI Ba(g) I(g) S9

10 Apparent "Cohesive Energy" / kj mol Thermodynamic Enthalpy Sum / kj mol -1 Figure S1: Plot of apparent cohesive energy (data listed in Tables 2 and S2) versus thermodynamic enthalpy sum (calculations not shown), showing lack of correlation; that is, this confirms that the listed apparent cohesive energy is not a cohesive energy, but actually a lattice enthalpy. S10

11 References (1) Cohen, E. R.; Cvitaš, T.; Frey, J. G.; Holmström, B.; Kuchitsu, K.; Marquardt, R.; Mills, I.; Pavese, F.; Quack, M.; Stohner, J.; Strauss, H. L.; Takami, M.; Thor, A. J., Quantities, Units and Symbols in Physical Chemistry - the IUPAC Green Book. 3rd ed.; IUPAC: RSC Publishing: Cambridge, UK, (2) Shinzato, Y. Energy expression for the chemical bond between atoms in hydrides and oxides. Nagoya University, (3) Yadav, D. S.; Singh, D. V., Phys. Scr. 2012, 85, (4) Jog, K. N.; Singh, R. K.; Sanyal, S. P., Physical Review B 1985, 31, (5) Li, C.; Lim Hoe, J.; Wu, P., J. Phys. Chem. Solids 2003, 64, (6) Palummo, M.; Bertoni, C. M.; Reining, L.; Finocchi, F., Physica B: Condensed Matter 1993, 185, (7) Hilsum, C.; Rose-Innes, A. C., Semiconducting III-V compounds. Pergamon Press: New York, (8) Doll, K.; Stoll, H., Physical Review B 1997, 56, (9) Thompson, M.; Shen, X.; Allen, P. B., Physical Review B 2009, 79, (10) Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y.; Humphreys, C. J.; Sutton, A. P., Physical Review B 1998, 57, (11) Hamad, B. A., European Physical Journal B 2009, 70, (12) Jenkins, H. D. B.; Roobottom, H. K., Lattice Energies. In CRC Handbook of Chemistry and Physics, Haynes, W. M., (Editor-in-Chief), Ed. CRC Press: Boca Raton, FL, (13) Outotec HSC Chemistry 8. (April, 2016), (14) von Szentpaly, L., J. Am. Chem. Soc. 2008, 130, S11

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