First-principles study of metastable phases and structural anomalies of iron, aluminum, zinc and cadmium under pressure.

Stable and metastable phases of Fe and Al and structural anomalies of Zn and Cd have been studied by epitaxial Bain path (EBP) and minimum path (MNP) first-principles procedures, based on finding equilibrium structures from minimizing the Gibbs free energy G with respect to structure at a given hydrostatic pressure p and temperature T. The main accomplishments are as follows. (1) This dissertation illustrates the effectiveness of the MNP procedure for finding stable and metastable phases of an element by studying four Bravais phases of Fe including body-centered tetragonal (bct), body-centered cubic (bcc), face-centered cubic (fcc) and rhombohedral (rh) phases. The determination of absolute stability using MNP is new; MNP finds all the elastic constants cij of a given state and the eigenvalues of the elastic constants matrix, which determine the absolute stability of the state. (2) We have extended our search for stable and metastable phases from zero temperature to finite temperature, which requires the calculations of the Debye temperature thetaD from cij in the case of no symmetry. The Debye theory is modified by introducing a parameter betaz that gives the fraction of the full Debye zero-point energy possessed by the actual dispersive mode frequencies. The value of the lattice parameter of fcc Al at low temperatures, a( T), is shown to be accurately determined by the modified Debye theory of lattice vibrations and first-principles total energy band calculations with the MNP procedure. (3) The existence of structural anomalies in hcp Zn and Cd has been shown from first-principles total-energy calculations using WIEN2k with the EBP procedure. Evaluation of the pressure dependence of various elastic quantities which are much more sensitive to the anomaly shows that the anomalies in hcp Zn and hcp Cd exist over a considerable range of pressure; several abrupt changes in the electron distribution are thereby indicated in that pressure range. (4) Calculations on the zone-center transverse optical phonon frequencies vTO (p) of hcp Zn, which found oscillatory behavior of vTO (p) in the pressure range of the anomalies, support the conclusions made in (3) on the structural anomalies. Based on this dissertation research four papers have been published in refereed journals.