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Structure-property relationships in solid state materials: a computational approach emphasizing chemical bonding

Stoltzfus, Matthew W.

Abstract Details

2007, Doctor of Philosophy, Ohio State University, Chemistry.
Density functional theory (DFT) calculations were performed to investigate the orbital interactions responsible for stereoactive lone pair distortions in ternary metal oxides. The calculations revealed that the stereoactivity of the lone pair is dependant upon the strength of interaction between the A-cation and the surrounding oxygen ligands. The resulting second order Jahn-Teller distortions are dependant upon the interactions and relative energies of the cation s, cation p, and oxygen p orbitals near the Fermi-level. The calculations also reveal fundamental differences in the orbital interactions responsible for the stereoactivity in Sn 2+, Pb 2+, and Bi 3+containing compounds. Ternary metal oxides involving Sr 2+, Pb 2+, and Ag +were also analyzed using DFT in order to evaluate the impact each cation plays on the band gap. Pb 2+and Ag +effectively reduce the band gap relative to Sr 2+by introducing electronically active states in close proximity to the valence band and conduction band edges. DFT calculations were performed on nine structural models of BaTaO 2N, SrTaO 2N, and CaTaO 2N revealing several similarities and differences in the local structure of each material. The calculations predict several trends: (i) a local cis configuration is more stable than a trans configuration, (ii) models involving a Ta 5+displacement are more stable than models in which the Ta 5+position is constrained to retain the inversion center of the undistorted octahedron, and (iii) the tendency for octahedral tilting increases from BaTaO 2N to SrTaO 2N to CaTaO 2N.
Patrick Woodward (Advisor)
227 p.

Recommended Citations

Citations

  • Stoltzfus, M. W. (2007). Structure-property relationships in solid state materials: a computational approach emphasizing chemical bonding [Doctoral dissertation, Ohio State University]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=osu1190087366

    APA Style (7th edition)

  • Stoltzfus, Matthew. Structure-property relationships in solid state materials: a computational approach emphasizing chemical bonding. 2007. Ohio State University, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=osu1190087366.

    MLA Style (8th edition)

  • Stoltzfus, Matthew. "Structure-property relationships in solid state materials: a computational approach emphasizing chemical bonding." Doctoral dissertation, Ohio State University, 2007. http://rave.ohiolink.edu/etdc/view?acc_num=osu1190087366

    Chicago Manual of Style (17th edition)