22

In one lecture at a recent MCR-X conference I was puzzled by a side-note "f-hole is critical to describe DoS of $\ce{IrO2}$ correctly." The context was DFT periodic plane-wave calculations with pseudization of the core electrons.

This implies that f-electrons are somewhat involved into chemistry of Ir. More precisely, it seems that polarizability of f-shell affects subsequent d-shell in somewhat dramatic way.

Could someone point at relevant articles, preferably discussing the matter from both ab initio and experimental perspective? Bonus points for generalization of the matter: d-electrons affect chemistry of heavy p-elements in no less way.

Ian Bush
  • 3,039
  • 1
  • 15
  • 28
permeakra
  • 21,572
  • 1
  • 55
  • 105
  • 5
    I'm not sure enough to post as an answer, but I think these two articles are relevant: "Conduction-electron screening in metallic oxides: Ir" http://journals.aps.org/prb/abstract/10.1103/PhysRevB.22.4680 and "Many-body effects in transition metals: role of the density of states" http://iopscience.iop.org/article/10.1088/0305-4608/6/12/015/meta – DavePhD Oct 12 '16 at 14:23
  • @DavePhD At the very least, it gives some food for thoughts. – permeakra Oct 16 '16 at 09:28

1 Answers1

3

"f-hole is critical to describe DoS of IrO2 correctly."

[...]

This implies, that f-electrons are somewhat involved into chemistry of Ir.

Perhaps naïvely, but I would dispute that the second statement follows from the first. While f-electrons are generally not critical for the chemical reactivity of molecules or materials, their inclusion indeed is critical for a proper description of the Density of States. The magnetic and optical properties, notably, can be derived from the DoS and depend directly from f electrons.

agaitaarino
  • 837
  • 7
  • 15