Cu^+和Ag^+叠氮盐晶体的周期性ab initio计算

Periodic Ab initio Calculations on Ag^+ and Cu^+ Azides

The energy bands,electronic structures of CuN3 and AgN3 crystallines were investigated by periodic ab initio method.The charge density projection shows that there are overlaps of isodensities between the terminal nitrogen and metallic ion,indicating that the metals and the azides are combined by covalent bonds.The crystal lattice energies are-781.05 and-840.83 kJ/mol for CuN3 and AgN3 respectively.These results approach the data obtained by Gray′s approximate method.The frontier crystal orbital mainly consists of the atomic orbital of azide′s terminal nitrogen.The energy gap for AgN3 is smaller than that of CuN3,and the highest occupied crystal orbitals of AgN-3 consist of both the atomic orbitals of the terminal nitrogen in azide and the silver ion,which facilitates the electron to leap from terminal nitrogen in azide to metallic ion directly.Hence silver azide is slightly more sensitive than copper azide.The elastic coefficients C11,C22 and C33 of CuN3 are predicted to be 96.52,96.86 and 154.06 GPa,C11 and C22 of AgN3 are 303.29 and 138.80 GPa.

The energy bands, electronic structures of CuN3 and AgN3 crystallines were investigated by periodic ab initio method. The charge density projection shows that there are overlaps of isodensities between the terminal nitrogen and metallic ion, indicating that the metals and the azides are combined by covalent bonds. The crystal lattice energies are -781.05 and -840. 83 kJ/mol for CuN3 and AgN3 respectively. These results approach the data obtained by Gray＇s approximate method. The frontier crystal orbital mainly consists of the atomic orbital of azide＇s terminal nitrogen. The energy gap for AgN3 is smaller than that of CuN3, and the highest occupied crystal orbitals of AgN3 consist of both the atomic orbitals of the terminal nitrogen in azide and the silver ion, which facilitates the electron to leap from terminal nitrogen in azide to metallic ion directly. Hence silver azide is slightly more sensitive than copper azide. The elastic coefficients Cll, C22 and C33 of CuN3 are predicted to be 96.52, 96.86 and 154. 06 GPa, Cll and C22 of AgN3 are 303.29 and 138.80 GPa.