We present ab initio quantum-mechanical molecular-dynamics simulations of the liquid-metal--amorphous-semiconductor transition in Ge. Our simulations are based on (a) finite-temperature density-functional theory of the one-electron states, (b) exact energy minimization and hence calculation of the exact Hellmann-Feynman forces after each molecular-dynamics step using preconditioned conjugate-gradient techniques, (c) accurate nonlocal pseudopotentials, and (d) Nos\'e dynamics for generating a canonical ensemble. This method gives perfect control of the adiabaticity of the electron-ion ensemble and allows us to perform simulations over more than 30 ps. The computer-generated ensemble describes the structural, dynamic, and electronic properties of liquid and amorphous Ge in very good agreement with experiment. The simulation allows us to study in detail the changes in the structure-property relationship through the metal-semiconductor transition. We report a detailed analysis of the local structural properties and their changes induced by an annealing process. The geometrical, bonding, and spectral properties of defects in the disordered tetrahedral network are investigated and compared with experiment.

Ab initio molecular-dynamics simulation of the liquid-metal-amorphous-semiconductor transition in germanium.

In recent years, ab initio molecular dynamics (MD) techniques have made a profound impact on the investigation of the structure of the electronic and dynamic properties of liquid and amorphous materials In this paper, recent developments in this field are reviewed and it is shown that the exact calculation of the electronic groundstate at each MD timestep is feasible using modern iterative matrix diagonalization algorithms Together with the use of ultrasoft pseudopotentials, ab initio MD simulations can be extended to open-shell transition metals with a high density of states at the Fermi-level The technique is applied to a number of interesting cases: (a) liquid simple metals (Li, Na, Al, Ge), (b) liquid transition metals (Cu, V), and (c) the transition from a liquid metal to an amorphous semiconductor by the rapid quenching of Ge

AB initio molecular dynamics for liquid metals

This review covers a wide range of experimental and theoretical studies of two-level or tunnelling states in glasses. Emphasis is on fundamental physics rather than a detailed comparison of experiment and theory. Sections cover the static and dynamic properties of tunnelling states, their contribution to thermal properties and their response to weak and strong electric and acoustic fields, both steady state and pulsed. A section on metallic glasses focuses on the importance of electron tunnelling-state interactions, and a final section illustrates approaches to a microscopic description by means of selected examples.

https://iopscience.iop.org/article/10.1088/0034-4885/50/12/003/pdf

Two-level states in glasses

First-principles molecular dynamics simulations have been performed on the solvation of Na+ in water. Consistent with the available experimental data, we find that the first solvation shell of Na+ contains on average 5.2 water molecules. A significant number of water exchanges between the first and second solvation shells are observed. However, the simulations are not long enough to reliably measure the rate of water exchange. Contrary to several previous studies, we do not find any effect of Na+ on the orientation of water molecules outside of the first solvation shell. Furthermore, the complete set of structural properties determined by first-principles molecular dynamics is not predicted by any of the known classical simulations.

The solvation of Na + in water: First-principles simulations

Although the majority of glasses in use in technology are complex mixtures of oxides or chalcogenides, there are numerous examples of pure substances-'glassformers'-that also fail to crystallize during cooling. Most glassformers are organic molecular systems, but there are important inorganic examples too, such as silicon dioxide and elemental selenium (the latter being polymeric). Bulk metallic glasses can now be made; but, with the exception of Zr50Cu50 (ref. 4), they require multiple components to avoid crystallization during normal liquid cooling. Two-component 'metglasses' can often be achieved by hyperquenching, but this has not hitherto been achieved with a single-component system. Glasses form when crystal nucleation rates are slow, although the factors that create the slow nucleation conditions are not well understood. Here we apply the insights gained in a recent molecular dynamics simulation study to create conditions for successful vitrification of metallic liquid germanium. Our results also provide micrographic evidence for a rare polyamorphic transition preceding crystallization of the diamond cubic phase.

Vitrification of a monatomic metallic liquid

Neutron diffraction techniques have been employed to obtain an accurate, high resolution correlation function for evaporated amorphous Ge. The structure of amorphous Ge is unlike that of any of the related crystalline polymorphs, but is much more accurately described in terms of a tetrahedrally bonded random network. The best fitting random network models, however, all predict too much structure in the correlation function at high r and severa; exhibit too narrow a distribution of bond angles.

A neutron diffraction study of the structure of evaporated amorphous germanium

The neutron scattering functions S(Q, nu ) for liquid nitrogen at 77.4K has been measured with a triple-axis spectrometer on the high flux reactor (HFR) at ILL Grenoble. Scattered neutron spectra were recorded at five Q values in the range between 4 AA-1 and 19 AA-1 using the constant-Q method. The scattering functions are compared to the predictions of a single-particle excitation model and are found to be in good agreement.

J.C. Dore

Papers

A neutron diffraction study of the structure of evaporated amorphous germanium

Single-particle excitations in liquid nitrogen