DOS/PDOS of Au2Te12(-4) Anion
Oxidation state of Au in (Et4N)4Au2Te12
from the viewpoint of the interaction between the Au3+ and [Te12]10- ions, each
"Au3+" ion of the [Au2Te12]4- anion receives about 2.8 electrons from the Te atoms directly
coordinated with it. Therefore, the most reasonable oxidation state of Au in the [Au2Te12]4- anion is
Au+ (d10), i.e., all the d-block levels of Au are completely filled in this anion.
To explore the above finding further, it is necessary to examine where the d-block levels of Au
lie in the energy spectrum of the [Au2Te12]4- anion. For this purpose, it is convenient to examine the
TDOS plot for the [Au2Te12]4- anion and the PDOS plot for the d-orbitals of the Au atoms. The following figure
presents such a plot calculated for the [Au2Te12]4- anion, where the TDOS is represented by a
solid line, and the PDOS of the Au d-orbitals by a dashed line. It is clear that the d-block levels of the
Au atoms lie well below the Fermi level, i.e., the highest occupied level of the [Au2Te12]4- anion.
Obviously, the observation reflects the fact that the 5d-level of Au lies considerably lower than
the 5p-level of Te. (Namely, -17.6 vs. -9.73 eV in the CRMM Basis set, -14.27 vs. -9.79 eV in the
ADF Basis set, and -15.08 vs. -13.2 eV in the Collected Basis set.) The present calculation is based on
the Collected Basis set, which provides the smallest energy difference between the Au 5d and the Te 5p
levels. The user may repeat calculations after decreasing this energy difference further (by either
raising the Te 5p level or lowering the Au 5d level). For any reasonable variation of the VSIP values
of the Au 5d and the Te 5p levels, the user will find that the above observation remains unchanged.
Thus, with some confidence, we may conclude that not only in the [Au2Te12]4- anion but also in other
binary compounds of Au and Te, the Au atoms should be monovalent.
DOS and PDOS plots for [Au2Te12]4- anion.
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