Premium
Gold Behaves as Hydrogen in the Intermolecular Self‐Interaction of Metal Aurides MAu 4 (M=Ti, Zr, and Hf)
Author(s) -
Jung Jaehoon,
Kim Hyemi,
Kim Jong Chan,
Park Min Hee,
Han YoungKyu
Publication year - 2011
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201000742
Subject(s) - crystallography , intermolecular force , metal , atomic orbital , chemistry , molecular orbital , hydrogen bond , binding energy , interaction energy , density functional theory , natural bond orbital , electron density , monomer , computational chemistry , atomic physics , electron , molecule , physics , organic chemistry , quantum mechanics , polymer
We performed density functional calculations to examine the intermolecular self‐interaction of metal tetraauride MAu 4 (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 (MH 4 ) 2 , the (μ‐Au) 3 C s 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 MAu 4 ‐MAu 4 than the interaction for MH 4 ‐MH 4 . There is a strong relationship between the dimeric interaction energy and the chemical hardness of its monomer for (MAu 4 ) 2 and (MH 4 ) 2 .