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Hydrogen multicentre bonds


The concept of a chemical bond stands out as a major development in the process of understanding how atoms are held together in molecules and solids. Lewis’ classical picture of chemical bonds as shared-electron pairs1 evolved to the quantum-mechanical valence-bond and molecular-orbital theories2,3, and the classification of molecules and solids in terms of their bonding type: covalent, ionic, van der Waals and metallic. Along with the more complex hydrogen bonds4 and three-centre bonds5,6, they form a paradigm within which the structure of almost all molecules and solids can be understood. Here, we present evidence for hydrogen multicentre bonds—a generalization of three-centre bonds—in which a hydrogen atom equally bonds to four or more other atoms. When substituting for oxygen in metal oxides, hydrogen bonds equally to all the surrounding metal atoms, becoming fourfold coordinated in ZnO, and sixfold coordinated in MgO. These multicentre bonds are remarkably strong despite their large hydrogen–metal distances. The calculated local vibration mode frequency in MgO agrees with infrared spectroscopy measurements7. Multicoordinated hydrogen also explains the dependence of electrical conductivity on oxygen partial pressure, resolving a long-standing controversy on the role of point defects in unintentional n-type conductivity of ZnO (refs 8–10).

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Figure 1: Coupling between the H 1s orbital and the Zn 4s ‘dangling bonds’ (Zn dbs) to form the hydrogen multicentre bond in ZnO.
Figure 2: Calculated DOS of hydrogen in the multicentre bond configuration HO in ZnO and MgO.
Figure 3: Three-dimensional visualization of the hydrogen multicentre bonds in ZnO and MgO.
Figure 4: Formation energy of substitutional hydrogen in ZnO and MgO.

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This work was supported in part by the NSF MRSEC Program under award no. DMR05-20415, and by AFOSR (contract no. F49620-02-1-1163) and ONR (contract no. N00014-02-C-0433) through subcontracts from the Palo Alto Research Center. It also made use of the CNSI Computing Facility under NSF grant no. CHE-0321368.

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Correspondence to Anderson Janotti or Chris G. Van de Walle.

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Janotti, A., Van de Walle, C. Hydrogen multicentre bonds. Nature Mater 6, 44–47 (2007).

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