Marius Hervé, Gael Privault, Elzbieta Trzop, Shintaro Akagi, Yves Watier, Serhane Zerdane, Ievgenia Chaban, Ricardo Guillermo Torres Ramirez, Céline Mariette, Alix Volte, Marco Cammarata, Hiroko Tokoro, Matteo Levantino, Eric Collet, Shin-ichi Ohkoshi
{"title":"光激发锰铁电荷转移材料在极性和相变状态下的超快结构动力学研究","authors":"Marius Hervé, Gael Privault, Elzbieta Trzop, Shintaro Akagi, Yves Watier, Serhane Zerdane, Ievgenia Chaban, Ricardo Guillermo Torres Ramirez, Céline Mariette, Alix Volte, Marco Cammarata, Hiroko Tokoro, Matteo Levantino, Eric Collet, Shin-ichi Ohkoshi","doi":"10.1002/ejic.202400371","DOIUrl":null,"url":null,"abstract":"The Rb0.94Mn0.94Co0.06[Fe(CN)6]0.98 material was designed to exhibit a 75 K wide thermal hysteresis around room temperature, associated with a bistability between the low temperature MnIIIFeII tetragonal phase and the high temperature MnIIFeIII cubic phase. We have recently shown that a single laser pulse can be used to drive, at room temperature, the photoinduced phase transition from the MnIIIFeII tetragonal phase to the MnIIFeIII cubic phase. By using a specific powder sample streaming technique, we could monitor by time‐resolved X‐ray diffraction how the ultrafast out‐of‐equilibrium dynamics, imposed by the structural relaxation around the local photoinduced charge transfer, changes with the fluence of the laser pulse. In this paper we present a detailed structural analysis of the crystalline reorganizations associated with the charge‐transfer in different regimes of photoexcitation. In the low excitation polaronic regime, the photoinduced charge transfer is local and accompanied by anisotropic distortion of the Mn coordination sphere and of the tetragonal lattice. In the high excitation regime, a macroscopic and cooperative charge‐transfer phase transition occurs towards the cubic lattice, where the coordination around the Mn reaches octahedral symmetry.","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.2000,"publicationDate":"2024-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Ultrafast Structural Dynamics of a Photoexcited Mn‐Fe Charge‐Transfer Material in the Polaronic and Phase Transition regimes\",\"authors\":\"Marius Hervé, Gael Privault, Elzbieta Trzop, Shintaro Akagi, Yves Watier, Serhane Zerdane, Ievgenia Chaban, Ricardo Guillermo Torres Ramirez, Céline Mariette, Alix Volte, Marco Cammarata, Hiroko Tokoro, Matteo Levantino, Eric Collet, Shin-ichi Ohkoshi\",\"doi\":\"10.1002/ejic.202400371\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"The Rb0.94Mn0.94Co0.06[Fe(CN)6]0.98 material was designed to exhibit a 75 K wide thermal hysteresis around room temperature, associated with a bistability between the low temperature MnIIIFeII tetragonal phase and the high temperature MnIIFeIII cubic phase. We have recently shown that a single laser pulse can be used to drive, at room temperature, the photoinduced phase transition from the MnIIIFeII tetragonal phase to the MnIIFeIII cubic phase. By using a specific powder sample streaming technique, we could monitor by time‐resolved X‐ray diffraction how the ultrafast out‐of‐equilibrium dynamics, imposed by the structural relaxation around the local photoinduced charge transfer, changes with the fluence of the laser pulse. In this paper we present a detailed structural analysis of the crystalline reorganizations associated with the charge‐transfer in different regimes of photoexcitation. In the low excitation polaronic regime, the photoinduced charge transfer is local and accompanied by anisotropic distortion of the Mn coordination sphere and of the tetragonal lattice. In the high excitation regime, a macroscopic and cooperative charge‐transfer phase transition occurs towards the cubic lattice, where the coordination around the Mn reaches octahedral symmetry.\",\"PeriodicalId\":38,\"journal\":{\"name\":\"European Journal of Inorganic Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":2.2000,\"publicationDate\":\"2024-08-22\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"European Journal of Inorganic Chemistry\",\"FirstCategoryId\":\"1\",\"ListUrlMain\":\"https://doi.org/10.1002/ejic.202400371\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"European Journal of Inorganic Chemistry","FirstCategoryId":"1","ListUrlMain":"https://doi.org/10.1002/ejic.202400371","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
摘要
Rb0.94Mn0.94Co0.06[Fe(CN)6]0.98材料被设计成在室温附近表现出75 K宽的热滞后,这与低温MnIIIFeII四方相和高温MnIIFeIII立方相之间的双稳态性有关。我们最近的研究表明,在室温下,单个激光脉冲可用于驱动从 MnIIIFeII 四方相到 MnIIFeIII 立方相的光诱导相变。通过使用特定的粉末样品流技术,我们可以用时间分辨 X 射线衍射法监测局部光诱导电荷转移周围的结构弛豫所引起的超快失衡动力学如何随激光脉冲的通量而变化。在本文中,我们对不同光激发状态下与电荷转移相关的晶体重组进行了详细的结构分析。在低激发极性条件下,光诱导的电荷转移是局部的,并伴随着锰配位层和四方晶格的各向异性畸变。在高激发机制下,向立方晶格发生了宏观和合作的电荷转移相变,锰周围的配位达到了八面体对称。
Ultrafast Structural Dynamics of a Photoexcited Mn‐Fe Charge‐Transfer Material in the Polaronic and Phase Transition regimes
The Rb0.94Mn0.94Co0.06[Fe(CN)6]0.98 material was designed to exhibit a 75 K wide thermal hysteresis around room temperature, associated with a bistability between the low temperature MnIIIFeII tetragonal phase and the high temperature MnIIFeIII cubic phase. We have recently shown that a single laser pulse can be used to drive, at room temperature, the photoinduced phase transition from the MnIIIFeII tetragonal phase to the MnIIFeIII cubic phase. By using a specific powder sample streaming technique, we could monitor by time‐resolved X‐ray diffraction how the ultrafast out‐of‐equilibrium dynamics, imposed by the structural relaxation around the local photoinduced charge transfer, changes with the fluence of the laser pulse. In this paper we present a detailed structural analysis of the crystalline reorganizations associated with the charge‐transfer in different regimes of photoexcitation. In the low excitation polaronic regime, the photoinduced charge transfer is local and accompanied by anisotropic distortion of the Mn coordination sphere and of the tetragonal lattice. In the high excitation regime, a macroscopic and cooperative charge‐transfer phase transition occurs towards the cubic lattice, where the coordination around the Mn reaches octahedral symmetry.
期刊介绍:
The European Journal of Inorganic Chemistry (2019 ISI Impact Factor: 2.529) publishes Full Papers, Communications, and Minireviews from the entire spectrum of inorganic, organometallic, bioinorganic, and solid-state chemistry. It is published on behalf of Chemistry Europe, an association of 16 European chemical societies.
The following journals have been merged to form the two leading journals, European Journal of Inorganic Chemistry and European Journal of Organic Chemistry:
Chemische Berichte
Bulletin des Sociétés Chimiques Belges
Bulletin de la Société Chimique de France
Gazzetta Chimica Italiana
Recueil des Travaux Chimiques des Pays-Bas
Anales de Química
Chimika Chronika
Revista Portuguesa de Química
ACH—Models in Chemistry
Polish Journal of Chemistry
The European Journal of Inorganic Chemistry continues to keep you up-to-date with important inorganic chemistry research results.