We investigate the adiabatic approximation to the exact-exchange kernel for calculating correlation energies within the adiabatic-connection fluctuation–dissipation framework of time-dependent density functional theory. A numerical study is performed on a set of systems having bonds of different character (H2 and N2 molecules, H-chain, H2-dimer, solid-Ar, and the H2O-dimer). We find that the adiabatic kernel can be sufficient in strongly bound covalent systems, yielding similar bond lengths and binding energies. However, for non-covalent systems, the adiabatic kernel introduces significant errors around equilibrium geometry, systematically overestimating the interaction energy. The origin of this behavior is investigated by studying a model dimer composed of one-dimensional, closed-shell atoms, interacting via soft-Coulomb potentials. The kernel is shown to exhibit a strong frequency dependence at small to intermediate atomic separation that affects both the low-energy spectrum and the exchange-correlation hole obtained from the corresponding diagonal of the two-particle density matrix.
Skip Nav Destination
Article navigation
14 May 2023
Research Article|
May 09 2023
Strengths and limitations of the adiabatic exact-exchange kernel for total energy calculations
Maria Hellgren
;
Maria Hellgren
a)
(Conceptualization, Data curation, Formal analysis, Funding acquisition, Investigation, Writing – review & editing)
1
Sorbonne Université, MNHN, UMR CNRS 7590, IMPMC
, 4 place Jussieu, 75005 Paris, France
a)Author to whom correspondence should be addressed: maria.hellgren@upmc.fr
Search for other works by this author on:
Lucas Baguet
Lucas Baguet
(Conceptualization, Data curation, Formal analysis, Investigation, Writing – review & editing)
2
CEA, DAM, DIF
, F-91297 Arpajon, France
3
Université Paris-Saclay, CEA, Laboratoire Matière en Conditions Extrêmes
, 91680 Bruyères-le-Châtel, France
Search for other works by this author on:
a)Author to whom correspondence should be addressed: maria.hellgren@upmc.fr
J. Chem. Phys. 158, 184107 (2023)
Article history
Received:
February 13 2023
Accepted:
April 24 2023
Citation
Maria Hellgren, Lucas Baguet; Strengths and limitations of the adiabatic exact-exchange kernel for total energy calculations. J. Chem. Phys. 14 May 2023; 158 (18): 184107. https://doi.org/10.1063/5.0146423
Download citation file:
Sign in
Don't already have an account? Register
Sign In
You could not be signed in. Please check your credentials and make sure you have an active account and try again.
Could not validate captcha. Please try again.
Sign in via your Institution
Sign in via your InstitutionPay-Per-View Access
$40.00
202
Views
Citing articles via
Related Content
Correlation energy functional and potential from time-dependent exact-exchange theory
J. Chem. Phys. (January 2010)
Spin-unrestricted random-phase approximation with range separation: Benchmark on atomization energies and reaction barrier heights
J. Chem. Phys. (April 2015)
Range-separated density-functional theory with random phase approximation applied to noncovalent intermolecular interactions
J. Chem. Phys. (June 2010)