Anisotropic valence→core x-ray fluorescence from a [Rh(en)3][Mn(N)(CN)5]•H2O single crystal:: Experimental results and density functional calculations
Anisotropic valence→core x-ray fluorescence from a [Rh(en)3][Mn(N)(CN)5]•H2O single crystal:: Experimental results and density functional calculations
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DOI：
10.1063/1.1419062
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发表时间：
2002-02-01
影响因子：
4.4
通讯作者：
Cramer, SP
中科院分区：
文献类型：
--
作者：
Bergmann, U;Bendix, J;Cramer, SP
记录了化合物[Rh(En)(3)][Mn(N)(CN)(5)]·H2O单晶不同方向发射的高分辨X射线荧光光谱。通过与密度泛函理论(DFT)电子结构计算的比较，对光谱进行了解释。Kβ(‘)线是沿Mn-N轴强极化的，可以看作是N(2s)-gt；Mn(1s)跃迁，角度依赖关系在偶极近似下是可以理解的。所谓的Kbeta(2，5)区有许多贡献，但主要是由Mn(4p)和C(2s)-->；Mn(1s)跃迁主导的。发现在1 eV以内的跃迁能分裂与计算的占据分子轨道的能分裂一致。计算的相对转移概率重现了实验观察到的趋势。(C)2002年美国物理研究所。
High resolution x-ray fluorescence spectra have been recorded for emission in different directions from a single crystal of the compound [Rh(en)(3)][Mn(N)(CN)(5)].H2O. The spectra are interpreted by comparison with density functional theory (DFT) electronic structure calculations. The Kbeta(') line, which is strongly polarized along the Mn-N axis, can be viewed as an N(2s)-->Mn(1s) transition, and the angular dependence is understood within the dipole approximation. The so-called Kbeta(2,5) region has numerous contributions but is dominated by Mn(4p) and C(2s)-->Mn(1s) transitions. Transition energy splittings are found in agreement with those of calculated occupied molecular orbitals to within 1 eV. Computed relative transition probabilities reproduce experimentally observed trends. (C) 2002 American Institute of Physics.