Hand Milling Induced Phase Transition for Marcasite-type Carbodiimide,Journal of the American Chemical Society

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Hand Milling Induced Phase Transition for Marcasite-type Carbodiimide
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2025-03-24 , DOI: 10.1021/jacs.5c00962
Yuzuki Yamamoto ₁ , Kazuki Kume ₁ , Suzuka Miyazaki ₁ , Ayako Shinozaki ₂ , Peng Song _{3,

4} , Sayed Sahriar Hasan ₄ , Kenta Hongo ₅ , Ryo Maezono ₄ , Hiroki Ubukata ₆ , Hiroshi Kageyama ₆ , Mikio Higuchi ₇ , Yuji Masubuchi ₇

Affiliation

While high-pressure phase transitions have been widely studied in inorganic compounds such as oxides and chalcogenides, relatively little attention has been given to compounds containing molecular anions, such as carbodiimides and cyanamides. This study investigates the phase transition of marcasite-type orthorhombic Ba_0.9M_0.1NCN carbodiimides, where a transformation to a CsCl-type tetragonal phase was observed at room temperature under hydrostatic pressure of 0.8 GPa (M = Ca) and 0.3 GPa (M = Sr). This transition, accompanied by an increase in the metal coordination under from 6 to 8, occurs at pressures significantly lower than those required for the high-pressure phase transitions of rock-salt-type metal halides and marcasite-type metal diantimonides. Remarkably, partial phase transitions were also induced by hand milling, a process that applies localized shear forces, distinct from the particle-crushing effects of high-energy ball milling. The transition mechanism, analyzed via variable-cell nudged elastic band (VCNEB) calculations, revealed that while the linear NCN^2– anions remain stable, the shear-sliding of Ba²⁺ cations and the rotation of NCN^2– anions are critical to the structural transformation. These findings underscore the potential of hand milling to effectively induce phase transitions in compounds containing linear molecular anions, offering new strategies for predicting and controlling such transitions in similar materials.

中文翻译：

马卡铁矿型碳二亚胺的手工铣削诱导相变

虽然在氧化物和硫纶等无机化合物中已广泛研究了高压相变，但对含有分子阴离子（如碳二亚胺和氰胺）的化合物的关注相对较少。本研究研究了黄铁矿型正交菱形 Ba_0.9M_0.1NCN 碳化二亚胺的相变，其中在室温下在 0.8 GPa （M = Ca）和 0.3 GPa （M = Sr）的静水压力下观察到向 CsCl 型四方相的转变。这种转变伴随着金属配位从 6 到 8 的增加，发生在明显低于岩盐型金属卤化物和白铁矿型金属二锑化物的高压相变所需的压力下。值得注意的是，部分相变也是由手磨引起的，手工铣削是一种施加局部剪切力的工艺，与高能球磨的颗粒粉碎效应不同。通过可变单元轻推弹性带（VCNEB）计算分析的过渡机制表明，虽然线性 NCN^2-阴离子保持稳定，但 Ba²⁺ 阳离子的剪切滑动和 NCN^2-阴离子的旋转对结构转变至关重要。这些发现强调了手铣在含有线性分子阴离子的化合物中有效诱导相变的潜力，为预测和控制类似材料中的此类转变提供了新的策略。

更新日期：2025-03-24

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