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</o:shapelayout></xml><![endif]--></head><body lang=EN-US link=blue vlink=purple><div class=WordSection1><p class=MsoNormal style='line-height:150%'><b><span style='font-size:14.0pt;line-height:150%;font-family:"Goudy Old Style","serif"'>Name:</span></b><span style='font-size:14.0pt;line-height:150%;font-family:"Goudy Old Style","serif"'> Douglas Wood<span style='color:#1F497D'> </span><b>Date:</b> Monday, April 25, 2011<span style='color:#1F497D'> </span><b>Time:</b> 1:00pm<span style='color:#1F497D'> </span><b>Place:</b> Chemical Engineering Conference Room<o:p></o:p></span></p><p class=MsoNormal><b><span style='font-size:14.0pt'>~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~</span></b><span style='font-size:16.0pt'><o:p></o:p></span></p><p class=MsoNormal align=center style='text-align:center'><b><span style='font-size:14.0pt'>Application of Electron Structure Calculations to the Migration of Oxygen through a Perovskite Membrane<o:p></o:p></span></b></p><p class=MsoNormal align=center style='text-align:center'><b><span style='font-size:14.0pt'><o:p> </o:p></span></b></p><h1 style='text-align:justify;line-height:200%'><span style='font-size:12.0pt;line-height:200%;font-family:"Times New Roman","serif";font-weight:normal'>The focus of this thesis is the application of electron structure calculations particularly density functional theory to the analysis of the process by which oxygen is able to migrate through a perovskite crystal. This property creates the possibility of using perovskite membranes to separate oxygen from air. This could be applied to the generation of syngas directly from natural gas without the need for a separate air separation unit,<o:p></o:p></span></h1><h1 style='text-align:justify;line-height:200%'><span style='font-size:12.0pt;line-height:200%;font-family:"Times New Roman","serif";font-weight:normal'>A perovskite has the nominal formula ABO<sub>3</sub> where A is a rare earth type cation and B is a transition type cation. The structure consists of the B cations arranged in a cube with the A cation in the center. The oxygen ions are located at the mid-point of each B-B cube edge and form an octahedron centered on each B cation.<o:p></o:p></span></h1><p class=MsoNormal style='mso-margin-top-alt:12.0pt;margin-right:0in;margin-bottom:3.0pt;margin-left:0in;text-align:justify;line-height:200%'>Any real perovskite crystal will contain a certain fraction of vacancies at the oxygen sites. Oxygen migrates through the crystal by jumping from a neighboring site to the vacancy. The permeability of the crystal is thus a function of the concentration of vacancies and the activation energy of the jump from a neighboring site to the vacancy. These properties can be modified by adding dopants for the A and B cations. The literature contains a substantial amount of experimental work on the effect of such dopants.<o:p></o:p></p><p class=MsoNormal style='mso-margin-top-alt:12.0pt;margin-right:0in;margin-bottom:3.0pt;margin-left:0in;text-align:justify;line-height:200%'>The overall migration process can be divided into components (i) the concentration of oxygen vacancies, (ii) the activation energy for a neighboring on-site oxygen atom to jump to the vacant site, (iii) the concentration of surface vacancies, and (iv) the processes by which oxygen ions transfer back and forth between the perovskite surface and the contiguous vapor space. <o:p></o:p></p><p class=MsoNormal style='mso-margin-top-alt:12.0pt;margin-right:0in;margin-bottom:3.0pt;margin-left:0in;text-align:justify;line-height:200%'>Using SrTiO<sub>3</sub> and LaCoO<sub>3</sub> as model compounds, DFT calculations have been used to (i) calculate various properties of the perovskite crystal, (ii) estimate the activation energy of a jump between an occupied oxygen site and an adjacent vacant oxygen site, (iii) predict the effects of various dopants at the A and B site and (iv) analyze the interaction of oxygen and carbon monoxide molecules with the perovskite surface.<o:p></o:p></p></div></body></html>