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自旋交叉分子中软 X 射线诱导激发自旋态捕获效应动力学的初步观察。

First glimpse of the soft x-ray induced excited spin-state trapping effect dynamics on spin cross-over molecules.

机构信息

Institut de Physique et de Chimie des Matériaux de Strasbourg, Université de Strasbourg, CNRS UMR 7504 23 rue du Loess, 67034 Strasbourg, France.

出版信息

J Chem Phys. 2013 Aug 21;139(7):074708. doi: 10.1063/1.4818603.

Abstract

The dynamics of the soft x-ray induced excited spin state trapping (SOXIESST) effect of Fe(phen)2(NCS)2 (Fe-phen) powder have been investigated by x-ray absorption spectroscopy (XAS) using the total electron yield method, in a wide temperature range. The low-spin (LS) state is excited into the metastable high-spin (HS) state at a rate that depends on the intensity of the x-ray illumination it receives, and both the temperature and the intensity of the x-ray illumination will affect the maximum HS proportion that is reached. We find that the SOXIESST HS spin state transforms back to the LS state at a rate that is similar to that found for the light induced excited spin state trapping (LIESST) effect. We show that it is possible to use the SOXIESST effect in combination with the LIESST effect to investigate the influence of cooperative behavior on the dynamics of both effects. To investigate the impact of molecular cooperativity, we compare our results on Fe-phen with those obtained for Fe{[Me2Pyrz]3BH}2 (Fe-pyrz) powder, which exhibits a similar thermal transition temperature but with a hysteresis. We find that, while the time constant of the dynamic is identical for both molecules, the SOXIESST effect is less efficient at exciting the HS state in Fe-pyrz than in Fe-phen.

摘要

通过使用总电子产额法的 X 射线吸收光谱(XAS),在很宽的温度范围内研究了 Fe(phen)2(NCS)2(Fe-phen)粉末的软 X 射线诱导激发自旋态捕获(SOXIESST)效应的动力学。低自旋(LS)态以与接收到的 X 射线照明强度有关的速率被激发到亚稳态高自旋(HS)态,温度和 X 射线照明强度都会影响达到的最大 HS 比例。我们发现,SOXIESST HS 自旋态以类似于光诱导激发自旋态捕获(LIESST)效应的速率返回到 LS 态。我们表明,有可能将 SOXIESST 效应与 LIESST 效应结合使用,以研究协同行为对这两种效应动力学的影响。为了研究分子协同作用的影响,我们将 Fe-phen 的结果与 Fe{[Me2Pyrz]3BH}2(Fe-pyrz)粉末的结果进行了比较,后者表现出相似的热转变温度,但具有滞后性。我们发现,尽管两个分子的动态时间常数相同,但 Fe-pyrz 中 SOXIESST 效应激发 HS 态的效率低于 Fe-phen。

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