Abstract
We performed density functional calculations to examine the intermolecular self-interaction of metal tetraauride MAu4 (M=Ti, Zr, and Hf) clusters. We found that the metal auride clusters have strong dimeric interactions (2.8-3.1 eV) and are similar to the metal hydride analogues with respect to structure and bonding nature. Similarly to (MH4) 2, the (μ-Au)3 Cs structures with three three-center two-electron (3c-2e) bonds were found to be the most stable. Natural orbital analysis showed that greater than 96 % of the Au 6s orbital contributes to the 3c-2e bonds, and this predominant s orbital is responsible for the similarity between metal aurides and metal hydrides (>99 % H 1s). The favorable orbital interaction between occupied Au 6s and unoccupied metal d orbitals leads to a stronger dimeric interaction for MAu4-MAu 4 than the interaction for MH4-MH4. There is a strong relationship between the dimeric interaction energy and the chemical hardness of its monomer for (MAu4)2 and (MH 4)2. Peculiar behavior of gold: Metal tetraaurides MAu4 (M=Ti, Zr, and Hf) are so named because gold behaves as a halogen. However, gold behaves as hydrogen in their corresponding dimeric system. Similarly to (MH4)2, the (μ-Au)3 Cs structures with three three-center two-electron (3c-2e) bonds are found to be the most stable.
Original language | English |
---|---|
Pages (from-to) | 868-872 |
Number of pages | 5 |
Journal | Chemistry - An Asian Journal |
Volume | 6 |
Issue number | 3 |
DOIs | |
State | Published - 1 Mar 2011 |
Keywords
- bond energy
- bond theory
- density functional calculations
- gold
- transition metals