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Hydrogen bond topology: order/disorder transitions in ice and the behavior of defects in a disordered ice lattice

Knight, Christopher J.
http://rave.ohiolink.edu/etdc/view?acc_num=osu1236788109

Abstract Details

2009, Doctor of Philosophy, Ohio State University, Chemistry.
To date, fifteen phases of ice have been discovered. Many of these phases occur in pairs consisting of a fully ordered member and a hydrogen bond (H-bond) disordered phase. The disordered phase contains the water oxygens in nearly the same positions as the fully ordered phase, but the orientations of hydrogens are disordered. Our research examines the phase transitions between members of these ordered/disordered pairs. These transitions are sluggish because they occur at such low temperatures that water molecules cannot easily rotate to rearrange the directions in which the hydrogen bonds point. It is defects in the ice lattice that make the transitions possible. For instance, ice Ih transforms to ice XI only when doped with hydroxide ions, but many questions linger about the mechanism since experiments suggest that hydroxide ions are not mobile near the transition temperature. In this dissertation, theoretical methods are introduced which are capable of describing the small energy differences among the innumerable H-bond configurations of the water molecules in ice. The theory uses input from periodic electronic density functional theory calculations for small unit cells to parameterize interactions in terms of the H-bond topology. This parameterization enables statistical mechanical calculations for systems large enough to approximate the thermodynamic limit. Our calculations were the first to confirm that ordinary ice, a disordered phase, transforms into a fully ordered counterpart, ice XI. For those disordered phases for which an ordered version has been experimentally characterized, our methods yield transition temperatures in good agreement with experiment. We also proposed a candidate structure to experimentalists for proton-ordered ice VI, for which an ordered version has yet to be observed. We have also extended these methods to describe the interactions of the H-bond topology with defects (ionic and orientational) and oxygen site-disorder. We have successfully constructed a model to describe a hydroxide ion in an ice Ih lattice. We found that the lowest-energy configuration surrounding the ion is the experimentally proposed ice XI structure. When coupled to the proton transfer events between hydroxide and water, our statistical mechanical simulations provide a description of defect diffusion within the disordered H-bond network.
Sherwin J. Singer, PhD (Advisor)
James V. Coe, PhD (Committee Member)
Russell M. Pitzer, PhD (Committee Member)
186 p.
Chemistry
ice; hydrogen bonds; order-disorder transformations; spin Hamiltonians; calorimetry; statistical mechanics; density functional theory; thermodynamic properties; phase diagrams; graph theory

Recommended Citations

Citations

  • Knight, C. J. (2009). Hydrogen bond topology: order/disorder transitions in ice and the behavior of defects in a disordered ice lattice [Doctoral dissertation, Ohio State University]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=osu1236788109

    APA Style (7th edition)

  • Knight, Christopher. Hydrogen bond topology: order/disorder transitions in ice and the behavior of defects in a disordered ice lattice. 2009. Ohio State University, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=osu1236788109.

    MLA Style (8th edition)

  • Knight, Christopher. "Hydrogen bond topology: order/disorder transitions in ice and the behavior of defects in a disordered ice lattice." Doctoral dissertation, Ohio State University, 2009. http://rave.ohiolink.edu/etdc/view?acc_num=osu1236788109

    Chicago Manual of Style (17th edition)

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© 2009, all rights reserved.
This open access ETD is published by The Ohio State University and OhioLINK.