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Cost and sensitivity of restricted active-space calculations of metal L-edge X-ray absorption spectra
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Theoretical Chemistry. Swami Ramanand Teerth Marathwada Univ, Sch Chem Sci, Nanded 431606, Maharashtra, India.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Theoretical Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Theoretical Chemistry.
Stockholm Univ, AlbaNova Univ Ctr, Dept Phys, SE-10691 Stockholm, Sweden.
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2016 (English)In: Journal of Computational Chemistry, ISSN 0192-8651, E-ISSN 1096-987X, Vol. 37, no 5, 477-486 p.Article in journal (Refereed) Published
Resource type
Text
Abstract [en]

The restricted active-space (RAS) approach can accurately simulate metal L-edge X-ray absorption spectra of first-row transition metal complexes without the use of any fitting parameters. These characteristics provide a unique capability to identify unknown chemical species and to analyze their electronic structure. To find the best balance between cost and accuracy, the sensitivity of the simulated spectra with respect to the method variables has been tested for two models, [FeCl6](3-) and [Fe(CN)(6)](3-). For these systems, the reference calculations give deviations, when compared with experiment, of 1 eV in peak positions, 30% for the relative intensity of major peaks, and 50% for minor peaks. When compared with these deviations, the simulated spectra are sensitive to the number of final states, the inclusion of dynamical correlation, and the ionization potential electron affinity shift, in addition to the selection of the active space. The spectra are less sensitive to the quality of the basis set and even a double- basis gives reasonable results. The inclusion of dynamical correlation through second-order perturbation theory can be done efficiently using the state-specific formalism without correlating the core orbitals. Although these observations are not directly transferable to other systems, they can, together with a cost analysis, aid in the design of RAS models and help to extend the use of this powerful approach to a wider range of transition metal systems.

Place, publisher, year, edition, pages
2016. Vol. 37, no 5, 477-486 p.
Keyword [en]
transition metals; X-ray absorption spectroscopy; multiconfigurational wavefunction; spin-orbit coupling; charge transfer
National Category
Theoretical Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-276263DOI: 10.1002/jcc.24237ISI: 000369176900002PubMedID: 26502979OAI: oai:DiVA.org:uu-276263DiVA: diva2:902098
Funder
Swedish National Infrastructure for Computing (SNIC), s00112-267 liu-2012-00060-46Carl Tryggers foundation Marcus and Amalia Wallenberg FoundationSwedish Research Council
Available from: 2016-02-10 Created: 2016-02-10 Last updated: 2017-08-16Bibliographically approved
In thesis
1. Electronic structure investigations of transition metal complexes through X-ray spectroscopy
Open this publication in new window or tab >>Electronic structure investigations of transition metal complexes through X-ray spectroscopy
2017 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Catalysts based on the first-row (3d) transition metals are commonly seen in chemical and biological reactions. To understand the role of the transition metal in the catalyst, the element specific technique core level spectroscopy is used to probe the electronic structure and geometric properties centered around the metal site. Different types of X-ray spectra can be applied to probe the metal 3d character orbitals involved in reactions, which make it possible to identify and characterize the reactive sites of samples in different forms. A detailed interpretation and understanding of the different X-ray spectra requires a unified method which can be used to model different types of X-ray spectra, e.g., soft and hard X-rays. In this thesis, theoretical investigations of the electronic structures of 3d transition metal complexes through X-ray spectroscopy are presented. The restricted active space method (RAS) is used to successfully reproduce different types of X-ray spectra by including all important spectral effects: multiplet structures, spin-orbit coupling, charge-transfer excitations, ligand field splitting and 3d-4p orbital hybridization. Different prototypes of molecules are adopted to test the applicability of the RAS theory.

The metal L edge X-ray absorption (XAS) spectra of low spin complexes [Fe(CN)6]n and [Fe(P)(ImH)2]n in ferrous and ferric oxidation state are discussed. The RAS calculations on iron L edge spectra of these comparing complexes have been performed to fingerprint the oxidation states of metal ion, and different ligand environments. The Fe(P) system has several low-lying spin states in the ground state, which is used as a model to identify unknown species by their spectroscopic fingerprints through RAS spectra simulations. To pave the route of understanding the electronic structure of oxygen evolution complex of Mn4CaO5 cluster, the MnII(acac)2 and MnIII(acac)3 are adopted as prototypical Mn-complexes. The 3d partial fluorescence yield-XAS are employed on the Mn L-edge in solution. Combining experiments and RAS calculations, primary questions related to the oxidation state and spin state are discussed.

The first application to simulate the metal K pre-edge XAS of mono-iron complexes and iron dimer using RAS method beyond the electric dipole is completed by implementing the approximate origin independent calculations for the intensities. The K pre-edge spectrum of centrosymmetric complex [FeCl6]n– ferrous state is discussed as s and a donor model systems. The intensity of the K pre-edge increases significantly if the centrosymmetric environment is broken, e:g:, when going from a six-coordinate to the four-coordinate site in [FeCl4]n. Distortions from centrosymmetry allow for 3d-4p orbital hybridization, which gives rise to electric dipole-allowed transitions in the K pre-edge region. In order to deliver ample electronic structure details with high resolution in the hard X-ray energy range, the two-photon 1s2p resonant inelastic X-ray scattering process is employed. Upon the above successful applications of one-photon iron L edge and K pre-edge spectra, the RAS method is extended to simulate and interpret the 1s2p resonant inelastic X-ray scattering spectra of [Fe(CN)6]n in ferrous and ferric oxidation states. The RAS applications on X-ray simulations are not restricted to the presented spectra in the thesis, it can be applied to the photon process of interest by including the corresponding core and valence orbitals of the sample.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2017. 73 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1541
Keyword
transition metal complexes, x-ray spectroscopy, electronic structures
National Category
Theoretical Chemistry Physical Chemistry
Research subject
Chemistry
Identifiers
urn:nbn:se:uu:diva-328072 (URN)978-91-513-0035-1 (ISBN)
Public defence
2017-10-06, Polhemssalen, Ång/10134, Ångströmlaboratoriet, Lägerhyddsvägen 1, Uppsala, 09:30 (English)
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Supervisors
Available from: 2017-09-14 Created: 2017-08-16 Last updated: 2017-09-14

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