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本文用ab initio研究了簇合物HeLi~(n+)(n=0,1)的几何构型和成键性质.在MP2(FULL)/6-31G,水平优化所得HeLi~+的平衡键长为0.2062nm,与实验值0.205nm十分吻合.比较了HeLi~+(X~1Σ~+和a~3Σ~+),HeLi(X~2Σ~+和a~4Π)以及HLi(X~1Σ~+)的稳定性.计算了HeLi~+基态的相关能,势能曲线和垂直激发态光谱.计算采用了6-31G,6-311G,6-311G(2df,2pd),6-311G(3df,2pd)和6-311+G(3df,2pd)基组;采用的方法包括MP2(FULL),MP4,MCSCF,MRSDCI,CCD和ST4CCD.计算表明,同价HeLi~(n+)中激发态的离解能均远比基态的大,其中HeLi~+(a~3Σ~+)的离解能最高(60.49KJ/mol),说明激发态是稳定束缚态.HeLi~+基态比等电子体HLi分子基态的稳定性小得多.HeLi~+由A~1Σ~+到B~1Π的垂直跃迁(3σ→1π)振子强度较大而垂直跃迁能较小.
In this paper, the geometrical configuration and bonding properties of cluster HeLi ~ (n +) (n = 0,1) have been studied by using ab initio. In MP2 (FULL) / 6-31G, the equilibrium bond length Is 0.2062 nm, which is in good agreement with the experimental value of 0.205 nm.Compared with HeLi ~ + (X ~ 1Σ ~ + and a ~ 3Σ ~ +), HeLi (X ~ 2Σ ~ + and a ~ 4Π) +) Is calculated.The correlation energies, potential energy curves and vertical excited states spectra of HeLi ~ + ground states are calculated.Using 6-31G, 6-311G, 6-311G (2df, 2pd), 6-311G (3df, 2pd) and 6-311 + G (3df, 2pd) groups. The methods used include MP2 (FULL), MP4, MCSCF, MRSDCI, CCD and ST4CCD. The calculated results show that the dissociation of the excited states in HeLi ~ (n + The dissociation energy of HeLi ~ + (a ~ 3Σ ~ +) is the highest (60.49KJ / mol), indicating that the excited state is a stable bound state.HeLi ~ + ground state ratio of the ground state of the HLi molecule The stability of HeLi ~ + is much stronger and the vertical transition energy is smaller due to the vertical transition (3σ → 1π) of HeLi ~ + from A ~ 1Σ ~ + to B ~ 1Π.