Slave mode expansion for obtaining ab initio interatomic potentials

Article

关键词: FUNCTIONAL PERTURBATION-THEORY;    TOTAL-ENERGY CALCULATIONS;    WAVE BASIS-SET;    MOLECULAR-DYNAMICS;    PHASE-TRANSITIONS;    FORCE-CONSTANTS;    SEMICONDUCTORS;    EFFICIENT;    CRYSTALS;    PHONONS;   

DOI  :  10.1103/PhysRevB.90.014308

来源: SCIE

【 摘 要 】

Here we propose an approach for performing a Taylor series expansion of the first-principles computed energy of a crystal as a function of the nuclear displacements. We enlarge the dimensionality of the existing displacement space and form new variables (i.e., slave modes) which transform like irreducible representations of the point group and satisfy homogeneity of free space. Standard group theoretical techniques can then be applied to deduce the nonzero expansion coefficients a priori. At a given order, the translation group can be used to contract the products and eliminate terms which are not linearly independent, resulting in a final set of slave mode products. While the expansion coefficients can be computed in a variety of ways, we demonstrate that finite difference is effective up to fourth order. We demonstrate the power of the method in the strongly anharmonic system PbTe. All anharmonic terms within an octahedron are computed up to fourth order. A proper unitary transformation demonstrates that the vast majority of the anharmonicity can be attributed to just two terms, indicating that a minimal model of phonon interactions is achievable. The ability to straightforwardly generate polynomial potentials will allow precise simulations at length and time scales which were previously unrealizable.

【 授权许可】

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