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Quantum chemical calculations of X-ray emission spectroscopy

Wadey, J.D.; Besley, Nicholas A.


J.D. Wadey

Nicholas A. Besley


The calculation of X-ray emission spectroscopy with equation of motion coupled cluster theory (EOM-CCSD), time dependent density functional theory (TDDFT) and resolution of the identity single excitation configuration interaction with second order perturbation theory (RI-CIS(D)) is studied. These methods can be applied to calculate X-ray emission transitions by using a reference determinant with a core-hole, and they provide a convenient approach to compute the X-ray emission spectroscopy of large systems since all of the required states can be obtained within a single calculation removing the need to perform a separate calculation for each state. For all of the methods, basis sets with the inclusion of additional basis functions to describe core orbitals are necessary, particularly when studying transitions involving the 1s or- bitals of heavier nuclei. EOM-CCSD predicts accurate transition energies when compared with experiment, however, its application to larger systems is restricted by its computational cost and difficulty in converging the CCSD equations for a core-hole reference determinant, which become increasing problematic as the size of the system studied increases. While RI-CIS(D) gives accurate transition energies for small molecules containing first row nuclei, its application to larger systems is limited by the CIS states providing a poor zeroth order reference for perturbation theory which leads to very large errors in the computed transition energies for some states. TDDFT with standard exchange-correlation functionals predicts transition energies that are much larger than experiment. Optimization of a hybrid and short-range cor- rected functional to predict the X-ray emission transitions results in much closer agreement with EOM-CCSD. The most accurate exchange-correlation functional identified is a modified B3LYP hybrid functional with 66% Hartree-Fock exchange, denoted B66LYP, which predicts X-ray emission spectra for a range of molecules including fluorobenzene, nitrobenzene, ace- tone, dimethyl sulfoxide and CF3Cl in good agreement with experiment.


Wadey, J., & Besley, N. A. (2014). Quantum chemical calculations of X-ray emission spectroscopy. Journal of Chemical Theory and Computation, 10(10), doi:10.1021/ct500566k

Journal Article Type Article
Publication Date Sep 4, 2014
Deposit Date Sep 9, 2015
Publicly Available Date Sep 9, 2015
Journal Journal of Chemical Theory and Computation
Print ISSN 1549-9618
Electronic ISSN 1549-9618
Publisher American Chemical Society
Peer Reviewed Peer Reviewed
Volume 10
Issue 10
Keywords TDDFT, X-ray emission
Public URL
Publisher URL
Copyright Statement Copyright information regarding this work can be found at the following address:
Additional Information This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Chemical Theory and Computation, copyright © American Chemical Society after peer review and technical editing by the publisher.
To access the final edited and published work see


XES-revised.pdf (541 Kb)

Copyright Statement
Copyright information regarding this work can be found at the following address:

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