Excited-state structure by time-resolved X-ray diffraction
Excited-state structure by time-resolved X-ray diffraction
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DOI：
10.1107/s0108767301017986
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发表时间：
2002-03-01
期刊：
影响因子：
--
通讯作者：
Coppens, P
中科院分区：
文献类型：
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作者：
Kim, CD;Pillet, S;Coppens, P
X射线晶体学传统上仅限于研究分子和固体的基态结构。最近的技术进步正在消除这一限制，正如这里所证明的时间分辨频闪研究的光诱导的50 μ s寿命激发三重态的[Pt-2（pop）（4）]（4-）离子[pop =焦磷酸，（H2 P2 O 5）（2-）]，在氦温度下进行同步辐射。在激发时Pt-Pt键缩短0.28（9）埃与所提出的涉及促进Pt-Pt反键dsigma* 电子到弱键p轨道的机制相容。收缩伴随着30度的分子旋转。这里描述的时间分辨衍射技术适用于晶体固态中的可逆光驱动过程。
X-ray crystallography has traditionally been limited to the study of the ground-state structure of molecules and solids. Recent technical advances are removing this limitation as demonstrated here by a time-resolved stroboscopic study of the photo-induced 50 mus lifetime excited triplet state of the [Pt-2(pop)(4)](4-) ion [pop = pyrophosphate, (H2P2O5)(2-)], performed at helium temperatures with synchrotron radiation. The shortening of the Pt-Pt bond by 0.28 (9) Angstrom upon excitation is compatible with the proposed mechanism involving promotion of a Pt-Pt antibonding dsigma* electron to a weakly bonding p orbital. The contraction is accompanied by a 3degrees molecular rotation. The time-resolved diffraction technique described here is applicable to reversible light-driven processes in the crystalline solid state.