Reference : Interatomic methods for the dispersion energy derived from the adiabatic connection f...
Scientific journals : Article
Physical, chemical, mathematical & earth Sciences : Chemistry
http://hdl.handle.net/10993/25128
Interatomic methods for the dispersion energy derived from the adiabatic connection fluctuation-dissipation theorem
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Tkatchenko, Alexandre mailto [Fritz-Haber-Institut der Max-Planck-Gesellschaft, Fara dayweg 4-6, 14195, Berlin, Germany]
Ambrosetti, Alberto [Fritz-Haber-Institut der Max-Planck-Gesellschaft, Fara dayweg 4-6, 14195, Berlin, Germany]
DiStasio, Jr [Department of Chemistry, Princeton University, Princeton , NJ 08544, USA]
2013
JOURNAL OF CHEMICAL PHYSICS
AMER INST PHYSICS
138
7
Yes (verified by ORBilu)
International
0021-9606
1305 WALT WHITMAN RD, STE 300, MELVILLE, NY 11747-4501 USA
[en] Interatomic pairwise methods are currently among the most popular and accurate ways to include dispersion energy in density functional theory calculations. However, when applied to more than two atoms, these methods are still frequently perceived to be based on ad hoc assumptions, rather than a rigorous derivation from quantum mechanics. Starting from the adiabatic connection fluctuation-dissipation (ACFD) theorem, an exact expression for the electronic exchange-correlation energy, we demonstrate that the pairwise interatomic dispersion energy for an arbitrary collection of isotropic polarizable dipoles emerges from the second-order expansion of the ACFD formula upon invoking the random-phase approximation (RPA) or the full-potential approximation. Moreover, for a system of quantum harmonic oscillators coupled through a dipole-dipole potential, we prove the equivalence between the full interaction energy obtained from the Hamiltonian diagonalization and the ACFD-RPA correlation energy. This property makes the Hamiltonian diagonalization an efficient method for the calculation of the many-body dispersion energy. In addition, we show that the switching function used to damp the dispersion interaction at short distances arises from a short-range screened Coulomb potential, whose role is to account for the spatial spread of the individual atomic dipole moments. By using the ACFD formula, we gain a deeper understanding of the approximations made in the interatomic pairwise approaches, providing a powerful formalism for further development of accurate and efficient methods for the calculation of the dispersion energy. (C) 2013 American Institute of Physics. [http://dx.doi.org/10.1063/1.4789814]
http://hdl.handle.net/10993/25128
10.1063/1.4789814
Article

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