The outcar file has the following:

total charge

# of ion s p d tot

------------------------------------------

1 0.865 1.796 0.000 2.661

2 0.865 1.796 0.000 2.661

3 0.865 1.796 0.000 2.661

4 0.865 1.796 0.000 2.661

The Wiki says:

The partial charge densities can be found in the OUTCAR

total charge

# of ion s p d tot

------------------------------------------

1 1.514 0.000 0.000 1.514

2 0.123 0.345 0.000 0.468

Here, the first column corresponds to the ion index 𝛼📷, the s, p, d,... columns correspond to the partial charges for 𝑙=0,1,2,⋯📷 defined as 𝜌𝛼𝑙=1𝑁𝑘∑𝑛𝑘𝑓𝑛𝑘∑𝑚=−𝑙𝑙|⟨𝑌𝑙𝑚𝛼|𝜙𝑛𝑘⟩|2📷

The ⟨𝑌𝑙𝑚𝛼|𝜙𝑛𝑘⟩📷 are obtained from the projection of the (occupied) KS orbitals |𝜙𝑛𝑘⟩📷 onto spherical harmonics that are non zero within spheres of a radius

RWIGS centered at ion 𝛼📷 and the last column is the sum ∑𝑙𝜌𝛼𝑙📷.

My question is: What do these really mean? For example, carbon should have 4 valence electrons but for graphite and porphyrin it reports 2.6 which seems too small. For (formally) Co(II) it reports 8.2, mostly from the d orbitals, which is way too big.

Can someone assist me in understanding these values?