Abstract
Bond lengths calculated for the coordination polyhedra in hydronitride molecules match average values observed for XN bonds involving main group X-cations in nitride crystals to within ∼0.04 Å. As suggested for oxide and sulfide molecules and crystals, the forces that determine the average bond lengths recorded for coordinated polyhedra in hydronitride molecules and nitride crystals appear to be governed in large part by the atoms that comprise the polyhedra and those that induce local charge balance. The forces exerted on the coordinated polyhedra by other parts of the structure seem to play a small if not an insignificant role in governing bond length variations. Bonded radii for the nitride ion obtained from theoretical electron density maps calculated for the molecules increase linearly with bond length as observed for nitride crystals with the rock salt structure. Promolecule radii calculated for the molecules correlate with bonded and ionic radii, indicating that the electron density distributions in hydronitride molecules possess a significant atomic component, despite bond type.
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Bader RFW, Beddall PM, Cade PE (1971) Partitioning and characterization of molecular charge distributions. J Am Chem Soc 93 (13): 3095–3107
Bader RFW (1990) Atoms in molecules: A quantum theory, pp 438. Oxford University Press, Oxford
Bartelmehs KL, Gibbs GV, Boisen Jr MB (1989) Bond-length and bonded-radii variations in sulfide molecules and crystals containing maingroup cations: A comparison with oxides. Am Mineral 74:620–626
Baur WH (1970) Bond length variation and distorted coordination polyhedra in inorganic crystals. Trans Am Crystallogr Assoc 6:129–155
Baur WH (1987) Effective ionic radii in nitrides. Crystallogr Rev 1:59–83
Buterakos LA (1990) Bond length and bonded radii variations in nitride molecules and crystals. MS Dissertation. Virginia Polytechnic Institute and State University, 28 pp. Blacksburg, Virginia
Brown ID, Shannon RD (1973) Empirical bond-strength — bond-length curves for oxides. Acta Crystallogr A29:266–282
D'Arco P, Julian MM, Gibbs GV (1989) Calculations of theoretical heat capacity curves for diamond. Eos 70(15):350
Dobbs KD, Hehre WJ (1986) Molecular orbital theory of the properties of inorganic and organometallic compounds 4.Extended basis sets for third- and fourth-row, main-group elements. J Computat Chem 7(3):359–378
Fajans K (1941) Polarization of ions and lattice distances. J Chem Phys 9:281–378
Finger LW, Gibbs GV (1985) A derivation of bonded radii from theoretical molecular charge distributions. Eos 66(18):356–357
Frisch MJ, Binkley JS, Schlegel HB, Rahavachari K, Melius CF, Martin RL, Stewart JJP, Bobrowicz FW, Rohlfing CM, Kahn LR, Defrees DJ, Seeger R, Whiteside RA, Fox DJ, Fleuder EM, Pople JA (1984) Gaussian 86. Carnegie-Mellon Quantum Chemistry Publishing Unit, Pittsburgh, PA
Geisinger KL, Gibbs GV (1981) SiSSi and SiOSi bonds in molecules and solids: a comparison. Phys Chem Minerals 7:204–210
Gibbs GV, Meagher EP, Newton MD, Swanson DK (1981) A comparison of experimental and theoretical bond length and angle variations for minerals, inorganic solids, and molecules. In: O'Keeffe M, Navrotsky A (eds). Struct Bonding 1:195–225. NewYork, Academic Press
Gibbs GV (1982) Molecules as models for bonding in silicates. Am Mineral 67:421–450
Gibbs GV, Boisen Jr MB (1986) Molecular mimicry of structure and electron density distributions in minerals. Mat Res Soc Symp Proc 73:515–527
Gibbs GV, D'Arco P, Boisen Jr MB (1987) Molecular mimicry of the bond length and angle variations in germinate and thiogermanate crystals: a comparison with variations calculated for carbon-, silicon-, and Sn-containing oxide and sulfide molecules. J Phys Chem 91:5347–5354
Gibbs GV, Finger LW, Boisen Jr MB (1987) Molecular mimicry of the bond length — bond strength variations in oxide crystals. Phys Chem Minerals 14:327–331
Gibbs GV, Boisen Jr MB, Downs RT, Lasaga AC (1988) Mathematical modeling of the structures and bulk moduli of TX2 quartz and cristobalite structure-types, T = C, Si, Ge and X = O, S. Mat Res Soc Symp Proc 121:155–165
Gibbs, GV, Spackman, MA, Boisen, MB Jr. (1992) Bonded and promolecule radii for molecules and crystals. Am Mineral 77, 741–750
Gourary BS, Adrian FJ (1960) Wave functions for electron-excess color centers in alkali halide crystals. Solid State Phys 10:127–247
Johnson O (1973) Ionic radii for spherical potential ions. I. Inorg Chem 12(4):780–785
Johnson O (1975) Ionic radii for spherical potential ions. II. Radii for rare earth, actinide, transition-metal and d10 cations. Chem Sc 7:5–10
Julian MM, and Gibbs GV (1985) Bonding in silicon nitrides. J Phys Chem 89(25):5476–5480
Julian MM, Gibbs GV (1988) Modeling the configuration about the nitrogen atom in methyl- and silyl-substituted amines. J Phys Chem 92(6):1444–1451
Lasaga AC, Gibbs GV (1987) Application of quantum mechanical potential surfaces to mineral physics calculations. Phys Chem Minerals 14:107–117
Lasaga AC, Gibbs GV (1988) Quantum mechanical potential surfaces and calculations on minerals and molecular clusters I: STO-3 G and 6–31 G* results. Phys Chem Minerals 16:29–41
Lindsay CG, Gibbs GV (1988) A molecular orbital study of bonding in sulfate molecules: Implications for sulfate crystal structures. Phys Chem Minerals 15:260–270
Newton MD, Gibbs GV (1980) Ab initio calculated geometries and charge distributions for H4SiO4 and H6Si2O7 compared with experimental values for silicates and siloxanes. Phys Chem Minerals 6:221–246
O'Keeffe M (1979) Madelung potentials and the sizes of ions in oxides and nitrides. Acta Crystallographica, A35:776–779
O'Keeffe M, Domengès B, Gibbs GV (1985) Ab initio molecular orbital calculation on phosphates: Comparison with silicates. J Phys Chem 89:2304–2309
Paschalis E, Weiss A (1969) Hartree-Fock-Roothaan wave functions, electron density distribution, diamagnetic susceptibility, dipole polarizability and antishielding factor for ions in crystals. Theor Chim Acta (Berlin) 13:381–408
Pauling L (1927) The sizes of ions and the structure of ionic crystals. J Am Chem Society 49(1):765–790
Pauling L (1929) The principles determining the structure of complex ionic crystals. J Am Chem Society 51:1010–1026
Prewitt CT (1982) Size and compressibility of ions at high pressure. Adv Earth Plant Sci 12:433–438
Prewitt CT (1985) Crystal Chemistry: past, present, and future. Am Mineral 70:443–454
Shannon RD, Prewitt CT (1969) Effective ionic radii in oxides and fluorides. Acta Crystallogr B25:925–936
Shannon RD (1976) Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallogr A32:751–767
Shannon, RD (1981) Bond distances in sulfides and a preliminary table of sulfide crystal radii. In: O'Keeffe M, Navrotsky A (eds) Structure and bonding in crystals. Vol II, pp 53–70. NewYork, Academic Press
Slater JC (1939) Introduction to Chemical Physics. New York, McGraw-Hill 521 pp
Slater JC (1965) Quantum theory of molecules and solids. Vol 2: Symmetry and energy bands in crystals. New York, McGraw-Hill
Spackman MA, Maslen EN (1986) Chemical properties from the promolecule. J Phys Chem 90:2020–2027
Zhang ZG, Boisen MB Jr, Finger LW, Gibbs GV (1985) Molecular mimicry of the geometry and charge density distribution of polyanions in borate minerals. Am Mineral 70:1238–1247
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Buterakos, L.A., Gibbs, G.V. & Boisen, M.B. Bond length variation in hydronitride molecules and nitride crystals. Phys Chem Minerals 19, 127–132 (1992). https://doi.org/10.1007/BF00198610
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DOI: https://doi.org/10.1007/BF00198610