Ab Initio Molecular Dynamics Simulation of Liquid and Amorphous Te

Contrary to almost all other elements, liquid and amorphous phases of pure tellurium have proven difficult to simulate using ab initio molecular dynamics. Standard density functional theory calculations yield structures in relatively poor agreement with available diffraction experiments at low temperature, especially regarding first neighbor distance and coordination number, which are strongly overestimated in the simulations. Tellurium being a key component of many phase change materials, this poor structural description of its disordered phases raises important issues about the ability of ab initio molecular dynamics to generate accurate structural models of amorphous phases.
In this work, we use ab initio molecular dynamics performed under constant volume (experimental values) conditions to simulate liquid Tellurium structure and dynamics along its density anomaly. We test different exchange correlation functionals and approximations, and show their influence on liquid and amorphous structures. In particular, we show that the treatment of dispersion forces is yielding a clear improvement over recent hybrid functional calculations [1], with significant local order modifications in both phases. Especially, the structure evolution along the density anomaly is shown to be related to the creation of many interconnections between Te chains, these chains having increasing lengths upon temperature reduction. In the amorphous phase, Te chains are almost perfectly isolated with specific dihedral angle distributions. These structural changes are reflected on dynamical properties, such as atomic diffusion coefficient and vibrational density of states. We then apply the same method to revisit the structure of some Te based alloys.
[1] J. Akola, R. O. Jones, S. Kohara, T. Usuki, and E. Bychkov, Phys. Rev. B 81, 094202 (2010).