AB-INITIO MO STUDY OF NA(NH3)(N) (N=1-6) CLUSTERS AND THEIR IONS - A SYSTEMATIC COMPARISON WITH HYDRATED NA CLUSTERS
AB-INITIO MO STUDY OF NA(NH3)(N) (N=1-6) CLUSTERS AND THEIR IONS - A SYSTEMATIC COMPARISON WITH HYDRATED NA CLUSTERS
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DOI：
10.1021/ja00119a032
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发表时间：
1995-04-12
影响因子：
15
通讯作者：
MOROKUMA, K
中科院分区：
文献类型：
--
作者：
HASHIMOTO, K;MOROKUMA, K
用从头算方法研究了Na（NH_3）（n）（n = 1-6）团簇及其离子的稳定性和结构，并与Na（H_2O）（n）团簇的稳定性和结构进行了系统的比较.中性和离子氨络合物与n大于或等于4具有内部结构，其中Na被NH3分子包围，而不是Na（H2O）（n）簇优选的表面结构。中性和离子团簇都通过Na-N键稳定;内部结构允许在第一溶剂化壳层中形成最大数量的这种键。计算的电离势作为溶剂分子数的函数与实验定量一致，并表现出与Na（H2O）（n）团簇表面结构不同的行为。在内部结构中，SOMO（单占据分子轨道）电子分布在团簇内部的Na和溶剂分子上和之间;预计将发生内部电离。
Stability and structure of Na(NH3)(n) (n = 1-6) clusters as well as their ions have been investigated by the ab initio MO method and systematically compared with those of Na(H2O)(n) clusters. Both neutral and ion ammonia complexes with n greater than or equal to 4 have an interior structure where Na is surrounded by NH3 molecules rather than a surface structure preferred by Na(H2O)(n) clusters. Both neutral and ion clusters are stabilized by the Na-N bonds; the interior structure allows formation of a maximum number of such bonds in the first solvation shell. The calculated ionization potential as a function of the number of solvent molecules is in good quantitative agreement with experiment and behaves differently from that of the surface structures of Na(H2O)(n) clusters. In the interior structure the SOMO (singly occupied molecular orbital) electron is distributed on and between Na and solvent molecules inside the cluster; interior ionization is expected to take place.