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Pré-Publication, Document De Travail Année : 2014

Excitation energies along a range-separated adiabatic connection

Résumé

We present a study of the variation of total energies and excitation energies along a range- separated adiabatic connection, which links the non-interacting Kohn-Sham electronic system to the physical interacting system by progressively switching on the electron-electron interactions whilst simultaneously adjusting a one-electron effective potential so as to keep the ground-state density constant. The interactions are introduced in a range-dependent manner, first introducing long-range, and then all-range, interactions as the physical system is approached. Reference data are reported for the He and Be atoms and the H 2 molecule, obtained by calculating the short-range effective potential at the full configuration-interaction level using Lieb's Legendre-transform approach. As the strength of the electron-electron interactions increases, the excitation energies, calculated for the partially interacting systems along the adiabatic connection, offer increasingly better approximations to the exact excitation energies. Importantly, the excitation energies calculated at an intermediate point of the adiabatic connection are much better approximations to the exact excitation energies than are the corresponding Kohn-Sham excitation energies. This is particularly evident in situations involving strong static correlation effects and states with multiple excitation character, such as the dissociating H2 molecule. These results highlight the usefulness of long-range interacting reference systems as a starting point for the calculation of excitation energies and are of interest for developing and analyzing practical approximate range-separated density-functional methodologies.
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Dates et versions

hal-00985367 , version 1 (29-04-2014)
hal-00985367 , version 2 (11-12-2014)

Identifiants

  • HAL Id : hal-00985367 , version 1

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Elisa Rebolini, Julien Toulouse, Andrew M. Teale, Trygve Helgaker, Andreas Savin. Excitation energies along a range-separated adiabatic connection. 2014. ⟨hal-00985367v1⟩
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