We report on the implementation of Dyson orbitals within the recently introduced frozen-core (fc) core–valence separated (CVS) equation-of-motion (EOM) coupled-cluster singles and doubles (CCSD) method, which enables efficient and reliable characterization of core-level states. The ionization potential (IP) variant of fc-CVS-EOM-CCSD, in which the EOM target states have one electron less than the reference, gives access to core-ionized states thus enabling modeling of X-ray photoelectron spectra (XPS) and its time-resolved variant (TR-XPS). Dyson orbitals are reduced quantities that can be interpreted as correlated states of the ejected/attached electron; they enter the expressions of various experimentally relevant quantities. In the context of photoelectron spectroscopy, Dyson orbitals can be used to estimate the strengths of photoionization transitions. We illustrate the utility of Dyson orbitals and fc-CVS-EOM-IP-CCSD by calculating XPS of the ground state of adenine and TR-XPS of the excited states of uracil.
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Stochastic many-body calculations of moiré states in twisted bilayer graphene at high pressures
We introduce three developments within the stochastic many-body perturbation theory: efficient evaluation of off-diagonal self-energy terms, construction of Dyson orbitals, and stochastic constrained random phase approximation. The stochastic approaches readily handle systems with thousands of atoms. We use them to explore the electronic states of twisted bilayer graphene (tBLG) characterized by giant unit cells and correlated electronic states. We document the formation of electron localization under compression; weakly correlated states are merely shifted in energy. We demonstrate how to efficiently downfold the correlated subspace on a model Hamiltonian with a screened frequency-dependent two-body interaction. For the 6° tBLG system, the onsite interactions are between 200 and 300 meV under compression. The Dyson orbitals exhibit spatial distribution similar to the mean-field single-particle states. Under pressure, the electron-electron interactions increase in the localized states; however, the dynamical screening does not fully balance the dominant bare Coulomb interaction.
more » « less- Award ID(s):
- 1945098
- NSF-PAR ID:
- 10361820
- Publisher / Repository:
- Nature Publishing Group
- Date Published:
- Journal Name:
- npj Computational Materials
- Volume:
- 8
- Issue:
- 1
- ISSN:
- 2057-3960
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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