Ru L2,3 XANES theoretical simulation with DFT: A test of the core-hole treatment
Ru L2,3 XANES theoretical simulation with DFT: A test of the core-hole treatment
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DOI：
10.1016/j.ssc.2012.08.004
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发表时间：
2012-10-01
影响因子：
2.1
通讯作者：
Pushkar, Yulia
中科院分区：
文献类型：
--
作者：
Alperovich, Igor;Moonshiram, Dooshaye;Pushkar, Yulia
采用密度泛函理论（DFT）方法对六氨合钌配合物[Ru（NH3）（6）]（3+）和“蓝色二聚体”水氧化催化剂cis，cis- [（bpy）（2）（H2O）（RuORuIII）-O-III（OH 2）（bpy）（2）]（4+）（bpy为2，2-联吡啶）的Ru L边X射线吸收近边结构（XANES）谱进行了模拟。两种计算方法进行了比较：模拟没有的核心孔和通过建模的核心孔内的Z + 1近似。计算和实验XANES光谱之间的良好协议实现不包括核心孔。用超越Z + 1近似的算法进行模拟，只有在标量相对论处理的框架下才有可能。用含时密度泛函（TD-DFT）方法计算了[Ru（NH3）（6）]（3+）模型化合物的Ru L边光谱.在[Ru（Mebimpy）（bpm）（H2O）]（2+）络合物的绿色函数形式体系（在FABR79.5软件包中实现）内的实空间全多重散射XANES建模中比较了三种不同的芯孔处理。后一种方法在不需要相对论效应的自旋轨道处理的情况下工作得很好。(c)2012爱思唯尔有限公司版权所有。
Density functional theory (DFT)-based relativistic calculations were performed to model the Ru L-edge X-ray absorption near edge structure (XANES) spectra of the hexaammineruthenium complex [Ru(NH3)(6)](3+) and "blue dimer" water oxidation catalyst, cis,cis- [(bpy)(2)(H2O)(RuORuIII)-O-III(OH2)(bpy)(2)](4+) (bpy is 2,2-bipyridine). Two computational approaches were compared: simulations without the core-hole and by modeling of the core-hole within the Z + 1 approximation. Good agreement between calculated and experimental XANES spectra is achieved without including the core-hole. Simulations with algorithms beyond the Z + 1 approximation were only possible in a framework of the scalar relativistic treatment. Time-dependent DFT (TD-DFT) was used to compute the Ru L-edge spectrum for [Ru(NH3)(6)](3+) model compound. Three different core-hole treatments were compared in a real-space full multiple scattering XANES modeling within the Green function formalism (implemented in the FEFF9.5 package) for the [Ru(Mebimpy)(bpm)(H2O)](2+) complex. The latter approaches worked well in cases where spin-orbit treatment of relativistic effects is not required. (c) 2012 Elsevier Ltd. All rights reserved.