Reference Energies for Valence Ionizations and Satellite Transitions

Journal of Chemical Theory and Computation, Journal Year: 2024, Volume and Issue: 20(11), P. 4751 - 4777

Published: May 22, 2024

Upon ionization of an atom or a molecule, another electron (or more) can be simultaneously excited. These concurrently generated states are called "satellites" shakeup transitions) as they appear in spectra higher-energy peaks with weaker intensity and larger width than the main associated single-particle ionizations. Satellites, which correspond to electronically excited cationic species, notoriously challenging model using conventional single-reference methods due their high excitation degree compared neutral reference state. This work reports 42 satellite transition energies 58 valence potentials (IPs) full configuration interaction quality computed small molecular systems. Following protocol developed for quest database [Véril, M.; Scemama, A.; Caffarel, Lipparini, F.; Boggio-Pasqua, Jacquemin, D.; Loos, P.-F. Wiley Interdiscip. Rev.: Comput. Mol. Sci. 2021, 11, e1517], these perturbative selection made iteratively (CIPSI) method. In addition, accuracy well-known coupled-cluster (CC) hierarchy (CC2, CCSD, CC3, CCSDT, CC4, CCSDTQ) is gauged against new accurate references. The performances various approximations based on many-body Green's functions (GW, GF2, T-matrix) IPs also analyzed. Their limitations correctly modeling transitions discussed.

Language: Английский

Fully Analytic G₀W₀ Nuclear Gradients

The Journal of Physical Chemistry Letters, Journal Year: 2025, Volume and Issue: unknown, P. 3672 - 3678

Published: April 4, 2025

In this letter, we present the first fully analytic derivation and implementation of nuclear gradients for G0W0 method. For this, leverage recently established connection between approach equation-of-motion unitary coupled-cluster theory charged excitations. Analytic are obtained through Lagrangian technique implemented validated by comparison with finite-difference calculations. G0W0, examine effect Tamm-Dancoff approximation evaluating screened Coulomb interaction. Finally, compare adiabatic ionization potential electron affinities to wave function-based electronic structure methods experimental values.

Language: Английский

Verification and validation of zero-point electron-phonon renormalization of the bandgap, mass enhancement, and spectral functions

npj Computational Materials, Journal Year: 2025, Volume and Issue: 11(1)

Published: May 3, 2025

Language: Английский