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Computational approaches and structural prediction of high pressure molecular solids



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The objective of this thesis is to study the crystal structures and electronic properties of solids at high pressure using state-of-the-art electronic structure computational methods. The thesis is divided into two main sections. The first part is to examine the performance and reliability of several current density functionals in the description of the electronic structures of small band gap materials and strongly correlated systems. The second part is to compare and evaluate two recently proposed first-principles methods for the prediction of stable structures of solids at high pressure. To accomplish the first goal, first-principle electronic structure calculations employing density functional theory (DFT) and several “correlation corrected” functionals calculations were used to investigate the properties of solid AlH3 and EuO at high pressure. The primary reason to study AlH3 is to resolve a discrepancy between previously predicted superconductivity behavior at 110 GPa but was not observed in experimental resistance measurements. The key to resolve the discrepancy is an accurate calculation of the valence and conduction band energies. The results shows that the Fermi surface is modified by the “improved” functionals over the previous calculations using “standard” gradient corrected functional. These changes in the Fermi surface topology removed the possibility of nesting of the electronic bands, therefore, solid AlH3 above 100 GPa is a poor metal instead of a superconductor. In the second system, we have studied EuO with highly localized electrons in the Eu 4f orbitals. A particular interest in this compound is the report of an anomalous isostructural phase transition with a significant volume reduction at 35-40 GPa and the relationship with the electronic state of Eu at high pressure. Using the Hubbard on-site repulsion model (LDA+U), we successfully predicted the insulator  metal transition of EuO at 12 GPa and the trend in the Mössbauer isomer shifts. However, the isostructural transition was not reproduced. The U on-site repulsion to localized Eu 4f orbtials helped to ameliorate some deficiencies of the PBE functional and improved the agreement with experimental observations but not all the properties were correctly reproduced. The second objective of this investigation is to predict energetically stable crystalline structures at high pressure. The reliability and relative efficiency of two recently proposed structure prediction methods, viz, Particle Swarm Optimization (PSO) and the Genetic Algorithm (GA) were critically examined. We applied the techniques to two separate systems. The first system is solid CS2. The motivation is that this compound was recently found to be a superconductor with a critical temperature of 6 K from 60 – 120 GPa. However, no crystalline structure was found by experiment in this pressure range. Our calculations suggest the energetic favorable structures contain segregated regions of carbon and sulfur atoms. The sulfur atoms adopt a planar closed pack arrangement forming 2D square or hexagonal networks and the carbon atoms tend to form hexagonal rings. A global minimum crystalline structure with structural features observed in the amorphous structure was found and shown to be superconductive. In the second case, we studied the possibility on the existence of Xe-halides (XeHn (H=Cl, Br and I, n = 1, 2 and 4)) compounds below 60 GPa. We reported the stability, crystal and electronic structures, vibrational and optical spectra of a number of stoichiometric crystalline polymorphs. We found that only XeCl and XeCl2 form thermodynamically stable compounds at pressure exceeding 60 GPa. A stable cubic fcc structure of XeBr2 was found to be a superconductor with critical temperature of 1.4 K. From these studies, we found both merits and shortcomings with the two structural prediction approaches. In the end, we proposed a hybrid approach to assure the same stable structure is predicted from both computational strategies.



Density Functional Theory, Structure prediction, High Pressure



Doctor of Philosophy (Ph.D.)


Physics and Engineering Physics




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