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  Ab Initio Wave Function-Based Determination of Element Specific Shifts for the Efficient Calculation of X-ray Absorption Spectra of Main Group Elements and First Row Transition Metals

Chantzis, A., Kowalska, J. K., Maganas, D., DeBeer, S., & Neese, F. (2018). Ab Initio Wave Function-Based Determination of Element Specific Shifts for the Efficient Calculation of X-ray Absorption Spectra of Main Group Elements and First Row Transition Metals. Journal of Chemical Theory and Computation, 14(7), 3686-3702. doi:10.1021/acs.jctc.8b00249.

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Chantzis, Agisilaos1, 2, Author           
Kowalska, Joanna K.1, Author
Maganas, Dimitrios1, 2, Author           
DeBeer, Serena1, Author
Neese, Frank1, 3, Author           
Affiliations:
1Max Planck Institute for Chemical Energy Conversion, Stiftstrasse 34-36, D-45470 Mülheim an der Ruhr, Germany, ou_persistent22              
2Research Group Manganas, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541709              
3Research Department Neese, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541710              

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 Abstract: In this study, a detailed calibration of the performance of modern ab initio wave function methods in the domain of X-ray absorption spectroscopy (XAS) is presented. It has been known for some time that for a given level of approximation, for example, using time-dependent density functional theory (TD-DFT) in conjunction with a given basis set, there are systematic deviations of the calculated transition energies from their experimental values that depend on the functional, the basis set, and the chosen treatment of scalar relativistic effects. This necessitates a linear correlation for a given element/functional/basis set combination to be established before chemical applications can be performed. This is a laborious undertaking since it involves sourcing trustworthy experimental data, lengthy geometry optimizations, and detailed comparisons between theory and experiment. In this work, reference values for the element-specific shifts of all the first-row transition metal atoms and the main group elements C, N, O, F, Si, P, S, and Cl have been computed by using a protocol that is based on the complete active space configuration interaction in conjunction with second-order N-electron valence state perturbation theory (CASCI/NEVPT2). It is shown that by extrapolating the results to the basis set limit of the method and taking into account scalar relativistic effects via the second-order Douglas–Kroll–Hess (DKH2) corrections, the predicted element shifts are on average less than 0.75 eV across all the absorption edges and a very good agreement between theory and experiment in all the studied XAS cases is observed. The transferability of these errors to molecular systems is thoroughly investigated. The constructed CASCI/NEVPT2 database of element shifts is used to evaluate the performance and to automatically calibrate prior to comparison with the experiment two commonly used methods in X-ray spectroscopy, namely, DFT/Restricted open shell configuration interaction singles (DFT/ROCIS) and TD-DFT methods.

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Language(s): eng - English
 Dates: 2018-03-072018-06-122018-07-10
 Publication Status: Published in print
 Pages: 17
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/acs.jctc.8b00249
 Degree: -

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Title: Journal of Chemical Theory and Computation
  Other : J. Chem. Theory Comput.
Source Genre: Journal
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Publ. Info: Washington, D.C. : American Chemical Society
Pages: - Volume / Issue: 14 (7) Sequence Number: - Start / End Page: 3686 - 3702 Identifier: ISSN: 1549-9618
CoNE: https://pure.mpg.de/cone/journals/resource/111088195283832