Response calculations based on an independent particle system with the exact one- particle density matrix: Excitation energies
Giesbertz, K., Gritsenko, O. V., & Baerends, E. J. (2012). Response calculations based on an independent particle system with the exact one- particle density matrix: Excitation energies. Journal of Chemical Physics, 136(9), Article 094104. https://doi.org/10.1063/1.3687344
Julkaistu sarjassa
Journal of Chemical PhysicsPäivämäärä
2012Tekijänoikeudet
© 2012 American Institute of Physics. Published in this repository with the kind permission of the publisher.
Adiabatic response time-dependent density functional theory (TDDFT) suffers from the restriction
to basically an occupied → virtual single excitation formulation. Adiabatic time-dependent density
matrix functional theory allows to break away from this restriction. Problematic excitations for
TDDFT, viz. bonding-antibonding, double, charge transfer, and higher excitations, are calculated
along the bond-dissociation coordinate of the prototype molecules H2 and HeH+ using the recently
developed adiabatic linear response phase-including (PI) natural orbital theory (PINO). The possibility
to systematically increase the scope of the calculation from excitations out of (strongly)
occupied into weakly occupied (“virtual”) natural orbitals to larger ranges of excitations is explored.
The quality of the PINO response calculations is already much improved over TDDFT even
when the severest restriction is made, to virtually the size of the TDDFT diagonalization problem
(only single excitation out of occupied orbitals plus all diagonal doubles). Further marked improvement
is obtained with moderate extension to allow for excitation out of the lumo and lumo+1,
which become fractionally occupied in particular at longer distances due to left-right correlation
effects. In the second place the interpretation of density matrix response calculations is elucidated.
The one-particle reduced density matrix response for an excitation is related to the transition
density matrix to the corresponding excited state. The interpretation of the transition density matrix
in terms of the familiar excitation character (single excitations, double excitations of various
types, etc.) is detailed. The adiabatic PINO theory is shown to successfully resolve the problematic
cases of adiabatic TDDFT when it uses a proper PI orbital functional such as the PILS functional.
...
Julkaisija
American Institute of PhysicsISSN Hae Julkaisufoorumista
0021-9606Julkaisu tutkimustietojärjestelmässä
https://converis.jyu.fi/converis/portal/detail/Publication/25527056
Metadata
Näytä kaikki kuvailutiedotKokoelmat
Samankaltainen aineisto
Näytetään aineistoja, joilla on samankaltainen nimeke tai asiasanat.
-
Approximate energy functionals for one-body reduced density matrix functional theory from many-body perturbation theory
Giesbertz, Klaas J. H.; Uimonen, Anna-Maija; van Leeuwen, Robert (Springer, 2018)We develop a systematic approach to construct energy functionals of the one-particle reduced density matrix (1RDM) for equilibrium systems at finite temperature. The starting point of our formulation is the grand potential ... -
Towards a novel energy density functional for beyond-mean-field calculations with pairing and deformation
Haverinen, Tiia; Kortelainen, Markus; Dobaczewski, J.; Bennaceur, K. (Jagellonian University, 2019)We take an additional step towards the optimization of the novel finite-range pseudopotential at a constrained Hartree–Fock–Bogolyubov level and implement an optimization procedure within an axial code using harmonic ... -
Model nuclear energy density functionals derived from ab initio calculations
Salvioni, G.; Dobaczewski, J.; Barbieri, C.; Carlsson, G.; Idini, A.; Pastore, A. (Institute of Physics, 2020)We present the first application of a new approach, proposed in (2016J.Phys.G:Nucl.Part.Phys.4304LT01) to derive coupling constants of the Skyrme energy density functional (EDF) fromab initioHamiltonian. By perturbing theab ... -
Disorder and interactions in systems out of equilibrium : the exact independent-particle picture from density functional theory
Karlsson, Daniel; Hopjan, Miroslav; Verdozzi, Claudio (American Physical Society, 2018)Density functional theory (DFT) exploits an independent-particle-system construction to replicate the densities and current of an interacting system. This construction is used here to access the exact effective potential ... -
Impact of the surface energy coefficient on the deformation properties of atomic nuclei as predicted by Skyrme energy density functionals
Ryssens, W.; Bender, M.; Bennaceur, Karim; Heenen, P.-H.; Meyer, J. (American Physical Society, 2019)Background: In the framework of nuclear energy density functional (EDF) methods, many nuclear phenomena are related to the deformation of intrinsic states. Their accurate modeling relies on the correct description of the ...
Ellei toisin mainittu, julkisesti saatavilla olevia JYX-metatietoja (poislukien tiivistelmät) saa vapaasti uudelleenkäyttää CC0-lisenssillä.