Simulation and analysis of melting behavior of local atomic structure of refractory metals vanadium

Abstract

By using large-scale atomic/molecular massively parallel simulator (LAMMPS) code, a molecular dynamics simulation is performed in the NPT ensemble at zero pressure to investigate the influence of melting rates γ on the evolutional characteristics of vanadium atomic structure such as body-centered cubic (BCC), hexagonal close-packed structure (HCP), face centered cubic (FCC), simple cubic (SC) and icosahedra (ICO) during the rapid melting of solid vanadium crystal at five different melting rates (γ1 = 1 × 1011 K/s, γ2 = 1 × 1012 K/s, γ3 = 1 × 1013 K/s, γ4 = 1 × 1014 K/s, γ5 = 1 × 1015 K/s), in which 16000 atoms in a cubic box under the periodic boundary condition are considered, and their motion equations are solved by Verlet's algorithm in the velocity form in time steps of 1 fs. Constant pressure P and temperature T are imposed by a modified Nose-Hoover method for both P and T variables, and an embedded-atom model (EAM) potential is utilized. For identifying the local atomic structures of liquid and solid vanadium at different temperatures, a polyhedral template matching method (PTMM) is used by measuring the root-mean square deviation (RMSD), in which clusters are classified as the topology of the local atomic environment without any ambiguity in the classification. Subsequently, the variation of the potential energy, entropy and Gibbs free energy of FCC, HCP, BCC and ICO vanadium clusters are calculated through ab initio MD simulation in the canonical ensemble (NVT) at selected temperatures, and the lowest-energy dynamic structure and its corresponding static heating structure are also shown in this paper. Based on the above calculated results, it is found that the melting point of refractory metal vanadium increases obviously with the increase of heating rate, but the heating rate only presents a limited effect on the population of atomic structure for each of BCC, HCP, FCC, SC and ICO. Namely, the temperature still plays a dominant role in the rapid melting process of V rather than heating rate. Moreover, the ab initio MD simulation and thermodynamics analysis further reveal that lots of ICO clusters of vanadium can exist stably in the liquid region rather than in solid crystal, which is not only due to its higher stability and longer lifetime than those of crystalline atomic clusters, but also because ICO possesses higher entropy and lower Gibbs free energy in high temperature liquid region.