论文标题

通过空间组不可还原衍生物的广义准时近似

The generalized quasiharmonic approximation via space group irreducible derivatives

论文作者

Mathis, Mark A., Khanolkar, Amey, Fu, Lyuwen, Bryan, Matthew S., Dennett, Cody A., Rickert, Karl, Mann, J. Matthew, Winn, Barry, Abernathy, Douglas L., Manley, Michael E., Hurley, David H., Marianetti, Chris A.

论文摘要

准时近似(QHA)是在恒定压力下相互作用的声子的最简单的非平底近似,将非谐度的影响带入了依赖温度的可观察到。尽管如此,由于在任意菌株下计算声子的复杂性,QHA通常会以额外的近似值实现,并且采用恒定应力边界条件的广义QHA尚未完全开发。在这里,我们制定了广义QHA,提供了一种实用算法,用于计算应变状态和其他可观察物,这是温度和真实压力的函数。我们通过采用不可还原的二阶位移衍生物及其应变依赖性来规避在任意菌株下计算声子的复杂性,这些衍生物及其应变依赖性,这些依赖性是有效地精确地计算出使用唯一的不可减少衍生化方法的。我们制定了两个互补的应变参数化:一个离散的应变网格插值和在对称应变中的泰勒串联膨胀。我们通过评估弹性恒定张量的温度和压力依赖性和使用三个交换相关函数的密度函数理论来说明我们的方法。将QHA结果与我们使用时域Brillouin散射和非弹性中子散射的弹性常数张量进行了比较。我们的不可还原衍生方法简化了广义QHA的实现,这将促进可重复的数据驱动的应用程序。

The quasiharmonic approximation (QHA) is the simplest nontrivial approximation for interacting phonons under constant pressure, bringing the effects of anharmonicity into temperature dependent observables. Nonetheless, the QHA is often implemented with additional approximations due to the complexity of computing phonons under arbitrary strains, and the generalized QHA, which employs constant stress boundary conditions, has not been completely developed. Here we formulate the generalized QHA, providing a practical algorithm for computing the strain state and other observables as a function of temperature and true stress. We circumvent the complexity of computing phonons under arbitrary strains by employing irreducible second order displacement derivatives of the Born-Oppenheimer potential and their strain dependence, which are efficiently and precisely computed using the lone irreducible derivative approach. We formulate two complementary strain parametrizations: a discretized strain grid interpolation and a Taylor series expansion in symmetrized strain. We illustrate our approach by evaluating the temperature and pressure dependence of the elastic constant tensor and the thermal expansion in thoria (ThO$_2$) using density functional theory with three exchange-correlation functionals. The QHA results are compared to our measurements of the elastic constant tensor using time domain Brillouin scattering and inelastic neutron scattering. Our irreducible derivative approach simplifies the implementation of the generalized QHA, which will facilitate reproducible, data driven applications.

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