Optimized Finite Difference Method for the Full-Potential XANES Simulations: Application to Molecular Adsorption Geometries in MOFs and Metal鈥揕igand Intersystem Crossing Transients

详细信息    查看全文

• 作者：Sergey A. Guda ; Alexander A. Guda ; Mikhail A. Soldatov ; Kirill A. Lomachenko ; Aram L. Bugaev ; Carlo Lamberti ; Wojciech Gawelda ; Christian Bressler ; Grigory Smolentsev ; Alexander V. Soldatov ; Yves Joly
• 刊名：Journal of Chemical Theory and Computation
• 出版年：2015
• 出版时间：September 8, 2015
• 年：2015
• 卷：11
• 期：9
• 页码：4512-4521
• 全文大小：566K
• ISSN：1549-9626

文摘

Accurate modeling of the X-ray absorption near-edge spectra (XANES) is required to unravel the local structure of metal sites in complex systems and their structural changes upon chemical or light stimuli. Two relevant examples are reported here concerning the following: (i) the effect of molecular adsorption on 3d metals hosted inside metal鈥搊rganic frameworks and (ii) light induced dynamics of spin crossover in metal鈥搊rganic complexes. In both cases, the amount of structural models for simulation can reach a hundred, depending on the number of structural parameters. Thus, the choice of an accurate but computationally demanding finite difference method for the ab initio X-ray absorption simulations severely restricts the range of molecular systems that can be analyzed by personal computers. Employing the FDMNES code [ Phys. Rev. B, 2001, 63, 125120] we show that this problem can be handled if a proper diagonalization scheme is applied. Due to the use of dedicated solvers for sparse matrices, the calculation time was reduced by more than 1 order of magnitude compared to the standard Gaussian method, while the amount of required RAM was halved. Ni K-edge XANES simulations performed by the accelerated version of the code allowed analyzing the coordination geometry of CO and NO on the Ni active sites in CPO-27-Ni MOF. The Ni鈥揅O configuration was found to be linear, while Ni鈥揘O was bent by almost 90掳. Modeling of the Fe K-edge XANES of photoexcited aqueous [Fe(bpy)₃]²⁺ with a 100 ps delay we identified the Fe鈥揘 distance elongation and bipyridine rotation upon transition from the initial low-spin to the final high-spin state. Subsequently, the X-ray absorption spectrum for the intermediate triplet state with expected 100 fs lifetime was theoretically predicted.