Metallic state in the vicinity of molecular orbital crystallization in the d1 thiospinel ZnTi2S4 prepared via a reductive ion-exchange reaction
Metallic state in the vicinity of molecular orbital crystallization in the d1 thiospinel ZnTi2S4 prepared via a reductive ion-exchange reaction
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通过还原离子交换反应制备的 d1 硫尖晶石 ZnTi2S4 分子轨道结晶附近的金属态
DOI：
10.1088/1361-648x/ac1369
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发表时间：
2021
期刊：
影响因子：
--
通讯作者：
Aruga Katori Hiroko
中科院分区：
文献类型：
--
作者：
Haraguchi Yuya;Arikai Hiroki;Aruga Katori Hiroko
采用低温离子交换法合成了一种新型的钛基硫尖晶石ZnTi 2S 4。ZnTi 2S 4具有金属基态的特征，表现为传导电子对热容和Pauli顺磁磁化率的贡献。这些观察结果与类似的基于Ti 3+的尖晶石MgTi 2 O 4的电子状态形成对比，其表现出与分子轨道结晶（MOC）相关的金属-绝缘体转变。此外，ZnTi 2S 4的磁化率在110 K附近出现了一个巨大的磁化率峰，这可能是由MOC涨落引起的. MgTi 2 O 4和ZnTi 2S 4电子态的差异可能是由于Ti 3d和p轨道（O：2 p和S：3 p）之间的重叠程度不同所致。在绝缘体-金属转变附近存在MOC态可能表明MOC中巡回的重要性。
A novel Ti 3+-based thiospinel ZnTi 2 S 4 is successfully synthesized via a low-temperature ion-exchange reaction. ZnTi 2 S 4 shows a signature of metallic ground state evidenced by a contribution of conduction electrons in the heat capacity and Pauli-like paramagnetic susceptibility. These observations contrast to the electronic state of similar Ti 3+-based spinel MgTi 2 O 4 exhibiting the metal–insulator transition associated with a molecular orbital crystallization (MOC). Furthermore, the magnetic susceptibility of ZnTi 2 S 4 shows a pseudogap-like behavior indicated by a vast peak in the magnetic susceptibility around 110 K, likely originating from the MOC fluctuation. The origin of the difference in the electronic states of MgTi 2 O 4 and ZnTi 2 S 4 would be due to the different magnitude of overlap between Ti 3d and p orbitals (O: 2p and S: 3p). The presence of a MOC state in the close vicinity of insulator-metal transition may suggest the importance of itinerancy in a MOC.