Citation: LIU Jiao, YAO Ping, NI Zhe-Ming, LI Yuan, SHI Wei. Jahn-Teller Effect of Cu-Mg-Al Layered Double Hydroxides[J]. Acta Physico-Chimica Sinica, ;2011, 27(09): 2088-2094. doi: 10.3866/PKU.WHXB20110923 shu

Jahn-Teller Effect of Cu-Mg-Al Layered Double Hydroxides

1.
Laboratory of Advanced Catalytic Materials, College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310032, P. R. China

Received Date: 9 May 2011
Available Online: 15 July 2011

We propose a periodic interaction model for the layered double hydroxides, Cu_xMg_3-xAl-LDHs (x=0-3). Based on density functional theory, the geometries of Cu_xMg_3-xAl-LDHs(x=0-3) were optimized using the CASTEP program. The Jahn-Teller effect and the stability were investigated by analyzing the geometric parameters, electronic arrangement, hydrogen-bonding, charge populations, and binding energies. The results show that the Jahn-Teller effect exists in the unfilled Cu²⁺ d orbital and also exists in the unfilled Mg²⁺ p orbital. The two orbitals affect the Jahn-Teller distortion of the metal ions. In Cu_xMg_3-xAl-LDHs(x=0-3), both aluminum and magnesium exist in stabilized octahedral forms. With an increase of Cu²⁺ in the layer the octahedral of copper changes from a flat configuration to a stable elongated configuration and the Jahn-Teller stabilization energy of the system gradually increases. In general, with an increase of Cu²⁺ in the layer the distortion caused by the Jahn-Teller effect weakens hydrogen-bonding and the electrostatic interactions between the host layer and the guest. The absolute value of the binding energy decreases and the chemical stability of the system decreases as well. This allows us to theoretically understand the Jahn-Teller effect better for the synthesis of copper-containing LDHs.
- Layered double hydroxide,
- Jahn-Teller effect,
- Density functional theory,
- Binding energy,
- Mulliken population
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