f-electrons in chemistry of heavy transition metals

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.





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> "f-hole is critical to describe DoS of IrO2 correctly."
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> This implies, that f-electrons are somewhat involved into chemistry of Ir.
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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.


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