A computational free energy reference for mechanically unstable phases

IF 1.9 3区 材料科学 Q4 CHEMISTRY, PHYSICAL
Hantong Chen , Qi-Jun Hong , Alexandra Navrotsky , Axel van de Walle
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引用次数: 0

Abstract

The CALPHAD (CALculation of PHAse Diagram) framework relies heavily on the availability of a well-defined free energy for all possible phases, including metastable and even mechanically unstable phases. However, for phases that exhibit mechanical instability, the determination of the free energy represents a challenge, both experimentally and computationally. This situation hinders the seamless integration of experimental and ab initio thermodynamic data. A newly developed method, named “inflection-detection”, provides a practical computational solution to this problem with a sound theoretical basis. Extending upon existing energy calculations at absolute zero, we provide further evidence of this method’s effectiveness by computing the temperature-dependent free energy references for 22 elemental structures involving mechanically unstable phases and showing that they are reasonably consistent with the (often wide) range of values determined in earlier experimental assessments. This suggests the feasibility of a reliable computation-based reference free energy standard for mechanically unstable pure elements.
机械不稳定相的计算自由能参考
CALPHAD(相图计算)框架在很大程度上依赖于所有可能相的自由能,包括亚稳态甚至机械不稳定相。然而,对于表现出机械不稳定性的相,自由能的测定在实验和计算上都是一个挑战。这种情况阻碍了实验和从头算热力学数据的无缝集成。一种名为“拐点检测”的新方法为这一问题提供了一种实用的计算解决方案,具有良好的理论基础。在现有的绝对零度下的能量计算的基础上,我们通过计算22个涉及机械不稳定相的元素结构的温度相关自由能参考值,进一步证明了该方法的有效性,并表明它们与早期实验评估中确定的值(通常很宽)范围相当一致。这表明为力学不稳定的纯元素建立可靠的基于计算的参考自由能标准是可行的。
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来源期刊
CiteScore
4.00
自引率
16.70%
发文量
94
审稿时长
2.5 months
期刊介绍: The design of industrial processes requires reliable thermodynamic data. CALPHAD (Computer Coupling of Phase Diagrams and Thermochemistry) aims to promote computational thermodynamics through development of models to represent thermodynamic properties for various phases which permit prediction of properties of multicomponent systems from those of binary and ternary subsystems, critical assessment of data and their incorporation into self-consistent databases, development of software to optimize and derive thermodynamic parameters and the development and use of databanks for calculations to improve understanding of various industrial and technological processes. This work is disseminated through the CALPHAD journal and its annual conference.
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