TY  - JOUR
AU  - Guda, Sergey A.
AU  - Guda, Alexander A.
AU  - Soldatov, Mikhail A.
AU  - Lomachenko, Kirill A.
AU  - Bugaev, Aram L.
AU  - Lamberti, Carlo
AU  - Gawelda, Wojciech
AU  - Bressler, Christian
AU  - Smolentsev, Grigory
AU  - Soldatov, Alexander V.
AU  - Joly, Yves
TI  - Optimized Finite Difference Method for the Full-Potential XANES Simulations: Application to Molecular Adsorption Geometries in MOFs and Metal–Ligand Intersystem Crossing Transients
JO  - Journal of chemical theory and computation
VL  - 11
IS  - 9
SN  - 1549-9626
CY  - Washington, DC
PB  - American Chemical Society (ACS)
M1  - PUBDB-2016-00018
SP  - 4512 - 4521
PY  - 2015
N1  - (c) American Chemical Society. Post referee full text in progress. Embargo for post referee full text 1 year from July 28, 2015.
AB  - 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)<sub>3</sub>]<sup>2+</sup> 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.
LB  - PUB:(DE-HGF)16
UR  - <Go to ISI:>//WOS:000361087600053
C6  - pmid:26575941
DO  - DOI:10.1021/acs.jctc.5b00327
UR  - https://bib-pubdb1.desy.de/record/292735
ER  -