
TY  - JOUR
A1  - Figgis, BN 
A1  - Reynolds, PA 
T1  - An X&#945; <I>ab initio</I> Calculation of the Charge and Spin-Density in Cs<sub>3</sub>Mo(NCS)<sub>6</sub> Crystals Compared With Experiment
JF  - Australian Journal of Chemistry
JO  - Aust. J. Chem.
Y1  - 1990
VL  - 43
IS  - 6
SP  - 1097
EP  - 1109
KW  - 
UR  - https://doi.org/10.1071/CH9901097 
N2  - We have performed ab initio discrete variational X&#945; calculations on a Cs18[Mo(NCS)6]15+ cluster, with the external electric field appropriate for a Cs3Mo(NCS)6 crystal. The calculations show both &#963; and &#960; bonding, and also the participation of diffuse molybdenum- centred  orbitals . Compared with the charge density experiment these effects are qualitatively correct but are underestimated. We performed further calculations successively removing the external electric field and the 18 Cs+ neighbours . The effects on the calculated metal- ligand bonding in the complex ion are negligible. This is not in agreement with experiment, so that these calculations which invoke only electrostatic effects and orthogonality with neighbouring ions and which also use only simple basis sets are not adequate. Further calculations on the Cr(NCS)63- and W(NCS)63- ions show increasing covalence from chromium to tungsten as expected. The spin transfer to the ligand is calculated to triple, but charge transfer is almost constant. 
ER  -

