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A liquid-liquid transition can exist in monatomic transition metals with a positive melting slope

机译:液态-液态过渡态可能存在于具有正熔融斜率的单原子过渡金属中

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摘要

Liquid-liquid transitions under high pressure are found in many elemental materials, but the transitions are known to be associated with either sp-valent materials or f-valent rare-earth elements, in which the maximum or a negative slope in the melting line is readily suggestive of the transition. Here we find a liquid-liquid transition with a positive melting slope in transition metal Ti from structural, electronic, and thermodynamic studies using ab-initio molecular dynamics calculations, showing diffusion anomaly, but no density anomaly. The origin of the transition in liquid Ti is a pressure-induced increase of local structures containing very short bonds with directionality in electronic configurations. This behavior appears to be characteristic of the early transition metals. In contrast, the late transition metal liquid Ni does not show the L-L transition with pressure. This result suggests that the possibility of the L-L transition decreases from early to late transition metals as electronic structures of late transition metals barely have a Jahn-Teller effect and bond directionality. Our results generalize that a phase transition in disordered materials is found with any valence band regardless of the sign of the melting slope, but related to the symmetry of electronic structures of constituent elements.
机译:在许多元素材料中都发现了高压下的液-液转变,但已知这些转变与sp价材料或f价稀土元素有关,其中熔解线的最大或负斜率是很容易暗示这种转变。在这里,我们从结构,电子和热力学研究中使用从头算的分子动力学计算,发现了过渡金属Ti中具有正熔融斜率的液-液过渡,显示出扩散异常,但没有密度异常。液体Ti中过渡的起源是压力诱导的局部结构的增加,该局部结构包含具有很短键的电子构型,具有方向性。这种行为似乎是早期过渡金属的特征。相反,后过渡金属液体Ni在压力下没有显示出L-L转变。该结果表明,由于早期过渡金属的电子结构几乎没有Jahn-Teller效应和键方向性,因此从早期过渡金属到晚期过渡金属的L-L过渡的可能性降低。我们的结果得出结论,无规材料的任何价带都存在相变,而与熔化斜率的符号无关,但与组成元素的电子结构的对称性有关。

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