Periodic energy decomposition analysis

A periodic extension of the energy decomposition analysis (pEDA) has been implemented in BAND. The natural orbitals for chemical valence (NOCV) is also available – at the gamma-point only.

With pEDA researchers can analyze in great detail the bonding interactions between fragments in periodic systems, for example:

  • molecules adsorbed on or absorbed in nanotubes (1D)
  • molecules adsorbed on surfaces (2D)
  • molecules absorbed in pores of MOFs (3D)

The bonding energy is decomposed in terms which are conceptually meaningful in chemistry: electrostatic attraction, Pauli repulsion, and orbital interactions. With NOCV the orbital interactions are further decomposed into the ones contributing the most to the chemical bonding between the two fragments. Furthermore spin-unrestricted fragments are possible with pEDA (see also the BAND analysis tutorials).

pEDA-NOCV

pEDA-NOCV: σ-donation from and π-back-donation to CO, adsorbed on Si(001) (top) and TiO2(110) (bottom).

M. Raupach and R. Tonner, A periodic energy decomposition analysis method for the investigation of chemical bonding in extended systems, J. Chem. Phys. 142, 194105 (2015).

Key concepts