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Equation-of-Motion Coupled-Cluster Theory to Model L-edge X-Ray Absorption and Photoelectron Spectra

preprint
submitted on 01.07.2020 and posted on 02.07.2020 by Marta L. Vidal, Pavel Pokhilko, Anna Krylov, Sonia Coriani
We present an extension of the equation-of-motion coupled-cluster singles and doubles (EOM-CCSD) theory for computing x-ray L-edge spectra, both in the absorption (XAS) and photoelectron (XPS) regimes. The approach is based on the perturbative evaluation of spin-orbit couplings using the Breit-Pauli Hamiltonian and nonrelativistic wave-functions described by the fc-CVS-EOM-CCSD ansatz (EOM-CCSD within the frozen-core core-valence separated (fc-CVS) scheme). The formalism is based on spinless one-particle density matrices. The approach is illustrated by modeling XAS and XPS of several model systems ranging from argon atoms to small molecules containing sulfur and silicon.

Funding

Independent Research Fund Denmark - Natural Sciences RP2 grant No. 7014-00258B

U.S. National Science Foundation No. CHE-1856342

History

Email Address of Submitting Author

soco@kemi.dtu.dk

Institution

Technical University of Denmark

Country

Denmark

ORCID For Submitting Author

0000-0002-4487-897X

Declaration of Conflict of Interest

A. I. K. is the President and a part-owner of Q-Chem, Inc.

Version Notes

Version submitted to J. Phys. Chem. Lett. on July 1, 2020

Exports