Gold Behaves as Hydrogen in the Intermolecular Self‐Interaction of Metal Aurides MAu4 (M=Ti,Zr, and Hf) |
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| Authors: | Jaehoon Jung Hyemi Kim Jong Chan Kim Dr Min Hee Park Dr Young‐Kyu Han |
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| Institution: | 1. Corporate R&D, LG Chem., Ltd. Research Park, Daejeon 305‐380 (Republic of Korea);2. Present addresses: Department of Advanced Materials Science, The University of Tokyo, Chiba 277‐8561 (Japan), RIKEN Advanced Science Institute, Wako, Saitama 351‐0198 (Japan);3. Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 305‐701 (Republic of Korea);4. Division of Materials Science, Korea Basic Science Institute, Daejeon 305‐333 (Republic of Korea), Fax: (+82)?42‐865‐3610 |
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| 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‐MAu4 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 (MH4)2. |
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| Keywords: | bond energy bond theory density functional calculations gold transition metals |
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