$d$-elements

The same applies to $d$ elements: the semi-core $p$ states and possibly the semi-core $s$ states should be treated as valence states. In most cases, reliable results however can be obtained even of the semi core states are kept frozen. As a rule of thumb the $p$ states should be treated as valence states, if their eigenenergy $\epsilon$ lies above $3$ Ry. Generally we recommend to use the following potentials:

Sc	154	Ti	178	V	192	Cr	227	Mn	269
		Ti_pv	222	V_pv	263	Cr_pv	265	Mn_pv	269
Sc_sv	222	Ti_sv	274	V_sv	263	Cr_sv	395	Mn_sv	387
		Zr	154			Mo	224	Tc	228
Y_sv	211	Zr_sv	229	Nb_pv	207	Mo_pv	224	Tc_pv	263
		Hf	220	Ta	223	W	223	Re	226
		Hf_pv	220	Ta_pv	223	W_pv	223	Re_pv	226
Fe	267	Co	267	Ni	269	Cu	290	Zn	276
Fe_pv	293	Co_pv	271	Ni_pv	367	Cu_pv	368
Fe_sv	390
Ru	213	Rh	228	Pd	250	Ag	249	Cd	274
Ru_pv	240	Rh_pv	250	Pd_pv	250
Os	228	Ir	210	Pt	230	Au	229	Hg	233
Os_pv	228			Pt_pv	294

Note: this table has been updated April 2009. Since computers are becoming ever more powerfull, we recommend to use the more accurate potentials whenever possible. Furthermore the potentials for the following elements have been update April/May 2009 to improve the $f$ scattering properties[119]: Cu, Mo-Ag, Pt, Au.

General comments:

• For X_pv pseudopotentials, the semi core $p$ states are treated as valence, whereas for X_sv pseudopotentials, the semi core $s$ states are treated as valence.

• X_pv potentials are required for early transition metals, but one can freeze the semi-core $p$ states for late transition metals (in particular noble metals).

• When to switch from X_pv potentials to the X potentials depends on the required accuracy and the row
  • for the $3d$ elements, even the Ti, V and Cr potentials give reasonable results, but should be used with uttermost care.
  • $4d$ elements are most problematic, and I advice to use the X_pv potentials up to Tc_pv.
  • $5d$ elements: $5p$ states are rather strongly localized (below 3 Ry), since the $4f$ shell becomes filled. One can use the standard potentials starting from Hf, but we recommend to perform test calculations.
• For some elements, additional X_sv potential are available but not listed in the table (e.g. Nb_sv, Mo_sv, Hf_sv). These potential usually have very similar cutoffs as the _pv potentials, and can be used as well. For HF type and hybrid functional calculations, we strongly recommend the use of the _sv and _pv potentials whenever possible.