We have developed a software package CALYPSO (Crystal structure AnaLYsis by Particle Swarm Optimization) to predict the energetically stable/metastable crystal structures of materials at given chemical compositions and external conditions (e.g., pressure). The CALYPSO method is based on several major techniques (e.g. particle-swarm optimization algorithm, symmetry constraints on structural generation, bond characterization matrix on elimination of similar structures, partial random structures per generation on enhancing structural diversity, and penalty function, etc) for global structural minimization from scratch. All of these techniques have been demonstrated to be critical to the prediction of global stable structure. We have implemented these techniques into the CALYPSO code. Testing of the code on many known and unknown systems shows high efficiency and high successful rate of this CALYPSO method [Wang et al., Phys. Rev. B 82 (2010) 094116][1]. In this paper, we focus on descriptions of the implementation of CALYPSO code and why it works.Comment: accepted in Computer Physics Communication

We have developed a method for crystal structure prediction from “scratch” through particle-swarm optimization (PSO) algorithm within the evolutionary scheme. PSO technique is different with the genetic algorithm and has apparently avoided the use of evolution operators (e.g., crossover and mutation). The approach is based on an efficient global minimization of free-energy surfaces merging total-energy calculations via PSO technique and requires only chemical compositions for a given compound to predict stable or metastable structures at given external conditions (e.g., pressure). A particularly devised geometrical structure parameter which allows the elimination of similar structures during structure evolution was implemented to enhance the structure search efficiency. The application of designed variable unit-cell size technique has greatly reduced the computational cost. Moreover, the symmetry constraint imposed in the structure generation enables the realization of diverse structures, leads to significantly reduced search space and optimization variables, and thus fastens the global structure convergence. The PSO algorithm has been successfully applied to the prediction of many known systems (e.g., elemental, binary, and ternary compounds) with various chemical-bonding environments (e.g., metallic, ionic, and covalent bonding). The high success rate demonstrates the reliability of this methodology and illustrates the promise of PSO as a major technique on crystal structure determination.

Room-temperature superconductivity has been a long-held dream and an area of intensive research. Recent experimental findings of superconductivity at 200 K in highly compressed hydrogen (H) sulfides have demonstrated the potential for achieving room-temperature superconductivity in compressed H-rich materials. We report first-principles structure searches for stable H-rich clathrate structures in rare earth hydrides at high pressures. The peculiarity of these structures lies in the emergence of unusual H cages with stoichiometries ${\mathrm{H}}_{24}$, ${\mathrm{H}}_{29}$, and ${\mathrm{H}}_{32}$, in which H atoms are weakly covalently bonded to one another, with rare earth atoms occupying the centers of the cages. We have found that high-temperature superconductivity is closely associated with H clathrate structures, with large H-derived electronic densities of states at the Fermi level and strong electron-phonon coupling related to the stretching and rocking motions of H atoms within the cages. Strikingly, a yttrium (Y) ${\mathrm{H}}_{32}$ clathrate structure of stoichiometry ${\mathrm{YH}}_{10}$ is predicted to be a potential room-temperature superconductor with an estimated $T_c$ of up to 303 K at 400 GPa, as derived by direct solution of the Eliashberg equation.

Hydrogen-rich compounds hold promise as high-temperature superconductors under high pressures. Recent theoretical hydride structures on achieving high-pressure superconductivity are composed mainly of H ₂ fragments. Through a systematic investigation of Ca hydrides with different hydrogen contents using particle-swam optimization structural search, we show that in the stoichiometry CaH ₆ a body-centered cubic structure with hydrogen that forms unusual “sodalite” cages containing enclathrated Ca stabilizes above pressure 150 GPa. The stability of this structure is derived from the acceptance by two H ₂ of electrons donated by Ca forming an “H ₄ ” unit as the building block in the construction of the three-dimensional sodalite cage. This unique structure has a partial occupation of the degenerated orbitals at the zone center. The resultant dynamic Jahn–Teller effect helps to enhance electron–phonon coupling and leads to superconductivity of CaH ₆ . A superconducting critical temperature (T _c ) of 220–235 K at 150 GPa obtained from the solution of the Eliashberg equations is the highest among all hydrides studied thus far.