Dear All,

I am getting confused with charges computed by Turbomole.

Say for example for Pt, the electronic configuration is

4d10, 5s2, 5p6, 4f14, 5d9, 6s1.

I used def2-SVP and ECP(60 e)

that gives (2xS + 6xP + 10xd = 18 e-) electrons for the computation.

followed by ridft-proper using pop mo x-y (pop lall mo x-y)

Now, i have charges for Pt in PtCl4.

Total s p d f

Pt 0.23841 2.81348 6.44446 8.47284 0.03081

Also for Pt in PtO2.

Pt 0.46431 3.22856 6.30666 7.92173 0.07874

Pt in PtCl4 and PtO2 have same oxidation state (+4).

1) Why do we get different numbers.

Assuming there is no backbonding from O to Pt.

2) Why do we get the occupation numbers more than

2 in S orbital and 6 in p orbital.

I can understand Mullikan charges are complicated,

but i used only small basis sets.

I checked also with lall option and no help.

Can anyone help me in understanding where i am

going wrong in understanding the concept.

Thanks in advance

KM