Theoretical Study of Geometric Structures for Ground-state Al_nC(n=2-7) Clusters

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With the aid of the molecular orbital DMol3 program,the energetics and electronic structures of several AlnC(n = 2-7) configurations have been searched and calculated by improved minimum energy paths(MEPs) by setting “imaging product”.A new high symmetry,supervalence isomer of Al5C cluster,i.e.,D5h-Al5C,at the local minimum in the MEPs is detected.Several parameters,such as binding energy,HOMO-LUMO energy gap,vertical electron detachment energy and electron affinity energy,are calculated to characterize and evaluate the stability of three Al5C configurations,i.e.,D5h-Al5C,Cs-Al5C and C1-Al5C.The results show that the D5h-Al5C cluster is the ground state structure instead of Cs-Al5C.Due to the formation of many central σ bonds after polymerizing for D5h-Al5C,the decrease of the energy for HOMO orbit results in more territory for HOMO electrons of dislocation effect,then the energy difference between HOMO and LUMO is increasing to enhance the stability of molecules to produce such supervalence structure of Al5C cluster.The configuration evolution between D5h-Al5C,Cs-Al5C and C1-Al5C and the synthesis preference in the mode of Al5 + C → Al5C reveals that the Cs-Al5C and C1-Al5C con-figurations are permissive to coexist with D5h-Al5C structure in energetics. With the aid of the molecular orbital DMol3 program, the energetics and electronic structures of several AlnC (n = 2-7) configurations have been searched and calculated by improved minimum energy paths (MEPs) by setting “imaging product”. A new High symmetry, supervalence isomer of Al5C cluster, ie, D5h-Al5C, at the local minimum in the MEPs is detected. Reference parameters such as binding energy, HOMO-LUMO energy gap, vertical electron detachment energy and electron affinity energy, are to characterize and evaluate the stability of three Al5C configurations, ie, D5h-Al5C, Cs-Al5C and C1-Al5C. The results show that the D5h-Al5C cluster is the ground state structure instead of Cs-Al5C. Due to the formation of many central σ bonds after polymerizing for D5h-Al5C, the decrease of the energy for HOMO orbit results in more territory for HOMO electrons of dislocation effect, then the energy difference between HOMO and LUMO is increasing to enhance the stability of molecules to produce such sup ervalence structure of Al5C cluster. The configuration evolution between D5h-Al5C, Cs-Al5C and C1-Al5C and the synthesis preference in the mode of Al5 + C → Al5C reveals that the Cs-Al5C and C1-Al5C con-figurations are permissive to coexist with D5h-Al5C structure in energetics.
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