New and efficient equation-of-motion coupled-cluster framework for core-excited and core-ionized states

Marta Lopez Vidal, Xintian Feng, Evgeny Epifanovsky, Anna I. Krylov, Sonia Coriani*

*Corresponding author for this work

Research output: Contribution to journalJournal articleResearchpeer-review

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We present a fully analytical implementation of the core-valence separation (CVS) scheme for the equation-of-motion (EOM) coupled-cluster singles and doubles (CCSD) method for calculations of core-level states. Inspired by the CVS idea as originally formulated by Cederbaum, Domcke and Schirmer, pure valence excitations are excluded from the EOM target space and the frozen-core approximation is imposed on the reference-state amplitudes and multipliers. This yields an efficient, robust, practical, and numerically balanced EOM-CCSD framework for calculations of excitation and ionization energies as well as state and transition properties (e.g., spectral intensities, natural transition and Dyson orbitals) from both the ground state and an excited state. The errors in absolute excitation/ionization energies relative to the experimental reference data are of the order of 0.2-3.0 eV, depending on the K-edge considered and on the basis set used, and the shifts are systematic for each edge. Compared to a previously proposed CVS scheme where CVS was applied as a posteriori projection only during the solution of the EOM eigenvalue equations, the new scheme is computationally cheaper. It also achieves better cancellation of errors, yielding similar spectral profiles but with absolute core excitation and ionization energies that are systematically closer to the corresponding experimental data. Among the presented results are calculations of transient-state X-ray absorption spectra, relevant for the interpretation of UV-pump/X-ray probe experiments.
Original languageEnglish
JournalJournal of Chemical Theory and Computation
Issue number5
Pages (from-to)3117-3133
Number of pages17
Publication statusPublished - 2019


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