Dissociation limit of the H2 molecule in the particle-hole random phase approximation

Mi-Song Dupuy (1) , Kyle Thicke (2)

1 LJLL (UMR_7598) - Laboratoire Jacques-Louis Lions
2 TAMU - Department of Mathematics [Texas]

In this work, we consider the particle-hole random phase approximation (phRPA), an approximation to the correlation energy in electronic structure, and show that the phRPA energy of the H2 molecule correctly dissociates. That is, as the hydrogen atoms are pulled apart, the phRPA energy of the system converges to twice the phRPA energy of a single hydrogen atom. Despite the simplicity of the H2 system, the correct dissociation of H2 is known to be a difficult problem for density functional approximations. As part of our result, we prove that the phRPA correlation energy is well-defined.

Domaines: Physique mathématique [math-ph]; Equations aux dérivées partielles [math.AP]

Mi-Song Dupuy, Kyle Thicke. Dissociation limit of the H2 molecule in the particle-hole random phase approximation. 2022. ⟨hal-03806571⟩