Dear Sten or dear other member of the ADF team,

We are studying spin-orbit coupling effects in TM complexes using ZORA
calculations and we

use TAPE15 to extract ZORA eigenvectors for the KS-orbitals of 3d-character.
The procedure

runs quite well and we were able to get interesting information for
tetrahedral and D2d distorted

tetrahedral complexes of Ni2+. However there is a problem with V(OH2)63+
complex which is

of S6 symmetry but we use C(I) because of pecularities with the ADF in the
present release.

In this symmetry the program lists all 10 double group A1/2.g species
without making use

of the Kramers degeneracy, otherwise the program would use only xy+, x2-y2+,
xz-, yz-, z2+

or alternatively the same space orbitals but with opposite spin. That is why
TAPE15 gives

210 eigenvectors and not 105 - the Kramers independent ones. Newetheless we
can leave

with this. However what is the assignment of the component of the
eigenvectors?

For example we have the 10 d-orbitals appearing from 25A1/2.g to 34A1/2.g;
in the list

of the A1.g symmetries the orbitals dz2, dx2-y2, dxy, dxz and dyz are Number
4, 7 10, 13, 16 from

the total of 105 functions without spin. How do you order the spin orbitals
in the eigenvectors:

dz2+dz2- dx2-y2+dx2-y2-dxy+dxy-dxz+dxz-dyz+dyz- or first the alfa spins for
the 105 orbitals

and than the 105 orbitals for beta spins from 106 to 210. We checked both
alternatives and neither of them

gives the correct eigenvalues, which we judge from an non-relativistic
calculation. In the higher symmetries

you always give the possibility to get the Klebsh-Gordon coefficients using
the command "print spinorbit".

The C(I) case you don't use this and obviously diagonalize the totat 210x210
matrix, this is highly iniconomic.

We will appreciate help in this matter,

Thanks in advance

M.Atanasov, C.Daul

Prof.Dr.M.Atanasov

Prof.Dr.C.Daul

Universite de Fribourg,

Switzerland

 
Received on 2004-03-25 21:05:44