Characterization of charge transfer excitations in hexacyanomanganate(III) with Mn K-edge resonant inelastic x-ray scattering.
Characterization of charge transfer excitations in hexacyanomanganate(III) with Mn K-edge resonant inelastic x-ray scattering.
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利用 Mn K 边共振非弹性 X 射线散射表征六氰基锰酸盐 (III) 中的电荷转移激发。
DOI：
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发表时间：
2010
影响因子：
4.4
通讯作者：
K. Gaffney
中科院分区：
文献类型：
--
作者：
D. Meyer;Xuena Zhang;U. Bergmann;K. Gaffney
我们使用硬x射线共振非弹性x射线散射（RIXS）和密度泛函理论（DFT）计算来表征K(3)Mn(CN)(6)中的电荷转移激发。RIXS测量和DFT计算的结合使我们能够表征配体-金属电子相互作用的强度，并将RIXS光谱中的拉曼共振分配给电荷转移激发。x射线激发能与主要来自Mn三维轨道的T（2g）和E(g)前边缘峰共振，我们观察到能量转移范围为2 ~ 12 eV的拉曼共振，这是由T（1u）对称已占据轨道填充1s核孔造成的。DFT计算表明，这些轨道主要表现出配体特征，支持将能量转移共振分配给配体到金属的电荷转移激发。我们的RIXS测量和DFT计算也表明，E(g)轨道自旋分裂了大约0.8 eV，尽管我们没有清楚地分辨出RIXS光谱中的两个吸收峰。我们还看到了用6545.0 eV入射光子激发金属到配体电荷转移（MLCT）激发的证据，大约比E(g)吸收峰高4 eV。6545.0 eV的共振发射谱显示出6.0 eV的能量转移共振，对应于T（2g）部分占据轨道的末态空穴。DFT计算表明，6545.0 eV的激发填充了一个以配体为主的未占据T(1u)-对称轨道。考虑到末态空穴的主要金属特征，我们将6.0 eV拉曼谐振分配给MLCT激发。这些测量证明了硬x射线RIXS表征配位化合物价电子结构的能力。
We use hard x-ray resonant inelastic x-ray scattering (RIXS) and density functional theory (DFT) calculations to characterize charge transfer excitations in K(3)Mn(CN)(6). The combination of RIXS measurements and DFT calculations allows us to characterize the strength of the ligand-metal electronic interaction and assign the Raman resonances in the RIXS spectra to charge transfer excitations. With x-ray excitation energies resonant with the T(2g) and E(g) pre-edge peaks derived predominantly from the Mn 3d orbitals, we observe Raman resonances in the energy transfer range from 2 to 12 eV, which results from the filling of the 1s core-hole from T(1u)-symmetry occupied orbitals. DFT calculations indicate that these orbitals exhibit primarily ligand character, supporting the assignment of the energy transfer resonances to ligand-to-metal charge transfer excitations. Our RIXS measurements and DFT calculations also indicate that the E(g)-orbital spin-splits by roughly 0.8 eV, though we do not cleanly resolve the two absorption peaks in the RIXS spectra. We also see evidence for a metal-to-ligand charge transfer (MLCT) excitation when exciting with a 6545.0 eV incident photon, roughly 4 eV above the E(g) absorption peaks. The 6545.0 eV resonant emission spectrum shows a 6.0 eV energy transfer resonance, which corresponds to a final state hole in the T(2g) partially occupied orbital. DFT calculations indicate that excitation at 6545.0 eV populates an unoccupied T(1u)-symmetry orbital of primarily ligand character. Given the predominantly metal character of the final state hole, we assign the 6.0 eV Raman resonance to a MLCT excitation. These measurements demonstrate the ability of hard x-ray RIXS to characterize the valence electronic structure of coordination compounds.
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影响因子：
15
作者：
Hocking, Rosalie K.;Wasinger, Erik C.;Solomon, Edward I.
通讯作者：
Solomon, Edward I.
影响因子：
15
作者：
Wasinger, EC;de Groot, FMF;Solomon, EI
通讯作者：
Solomon, EI
(L)2[Cu2(S2)n]2 配合物的 X 射线吸收光谱和理论研究：二硫键与二硫键 (*1-) 键合。
影响因子：
15
作者：
Sarangi,Ritimukta;York,JohnT;Helton,MatthewE;Fujisawa,Kiyoshi;Karlin,KennethD;Tolman,WilliamB;Hodgson,KeithO;Hedman,Britt;Solomon,EdwardI
通讯作者：
Solomon,EdwardI
Mn K 吸收前边的共振非弹性 X 射线散射 (RIXS) 光谱 - 3d 轨道的直接探针。
DOI：
10.1016/j.jpcs.2005.09.012
发表时间：
2005
期刊：
The Journal of physics and chemistry of solids
影响因子：
--
作者：
Glatzel,Pieter;Yano,Junko;Bergmann,Uwe;Visser,Hendrik;Robblee,JohnH;Gu,Weiwei;deGroot,FrankMF;Cramer,StephenP;Yachandra,VittalK
通讯作者：
Yachandra,VittalK