title: Optimized Finite Difference Method for the Full-Potential XANES Simulations: Application to Molecular Adsorption Geometries in MOFs and Metal-Ligand Intersystem Crossing Transients.
abstract: 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-organic frameworks and (ii) light induced dynamics of spin crossover in metal-organic 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-CO configuration was found to be linear, while Ni-NO was bent by almost 90°. Modeling of the Fe K-edge XANES of photoexcited aqueous [Fe(bpy)3](2+) with a 100 ps delay we identified the Fe-N 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.
authors.forename: Sergey A
authors.initials: SA
authors.lastname: Guda
authors.forename: Alexander A
authors.initials: AA
authors.lastname: Guda
authors.forename: Mikhail A
authors.initials: MA
authors.lastname: Soldatov
authors.affiliation: Department of Chemistry, NIS and CrisDi Centers, Turin University and INSTM Reference Center , 10125 Turin, Turin, Italy.
authors.forename: Kirill A
authors.initials: KA
authors.lastname: Lomachenko
authors.forename: Aram L
authors.initials: AL
authors.lastname: Bugaev
authors.affiliation: Department of Chemistry, NIS and CrisDi Centers, Turin University and INSTM Reference Center , 10125 Turin, Turin, Italy.
authors.forename: Carlo
authors.initials: C
authors.lastname: Lamberti
authors.affiliation: European XFEL, Albert-Einstein-Ring 19, 22761 Hamburg, Germany.
authors.forename: Wojciech
authors.initials: W
authors.lastname: Gawelda
authors.affiliation: European XFEL, Albert-Einstein-Ring 19, 22761 Hamburg, Germany.|The Hamburg Centre for Ultrafast Imaging (CUI), Universität Hamburg , Luruper Chaussee 149, 22761 Hamburg, Germany.
authors.forename: Christian
authors.initials: C
authors.lastname: Bressler
authors.affiliation: Paul Scherer Institute, Villigen, 5232, Switzerland.
authors.forename: Grigory
authors.initials: G
authors.lastname: Smolentsev
authors.forename: Alexander V
authors.initials: AV
authors.lastname: Soldatov
authors.affiliation: Inst NEEL, Université Grenoble Alpes , 38042 Grenoble, France.|Institut NEEL, CNRS , 38042 Grenoble, France.
authors.forename: Yves
authors.initials: Y
authors.lastname: Joly