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

02 July 2020, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


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.


Spin-orbit coupling
Inner-shell 2p spectra
core-valence separation
Breit-Pauli Hamiltonian
L-edge X-ray absorption spectroscopy
XPS binding energy
Coupled Cluster Theory

Supplementary materials

L-edges SI


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