title: Gold behaves as hydrogen in the intermolecular self-interaction of metal aurides MAu4 (M = Ti, Zr, and Hf).
abstract: 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).
authors.affiliation: Corporate R&D, LG Chem., Ltd. Research Park, Daejeon 305-380, Republic of Korea.
authors.forename: Jaehoon
authors.initials: J
authors.lastname: Jung
authors.forename: Hyemi
authors.initials: H
authors.lastname: Kim
authors.forename: Jong Chan
authors.initials: JC
authors.lastname: Kim
authors.forename: Min Hee
authors.initials: MH
authors.lastname: Park
authors.forename: Young-Kyu
authors.initials: YK
authors.lastname: Han