HeLi^(n+)(n=0,1)簇合物的稳定性和垂直激发态光谱  

The Stability and the Vertical Excited States of Elemental Cluster HeLi^(n+) (n = 0,1)

作　　者：龙建君[1] 张敬来[2] 田安民[2] 

机构地区：[1]遵义医学院化学教研室,遵义563003 [2]四川大学化学系,成都610064

出　　处：《化学学报》1997年第9期833-838,共6页Acta Chimica Sinica

基　　金：高等学校博士学科点专项基金;国家自然科学基金(批准号:29473108)资助课题。

摘　　要：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.The equilibrium geometric structures of the elemental clusters HeLin+ ( n = 0,1) have been optimized by using ab initio and analytic energy gradients at the MP2(FULL) /6 - 31G * *level The stabilities were studied for HeLi (X2∑+ ), HeLi (a4II), HeLi+ (X1()+) and HeLi+(a3∑+). The correlative energies and potential curves of the ground state (X1∑+) of HeLi+ were also calculated using the 6-311G* * ,6-311G(2df,2pd),6-311G(3df,2pd) and 6-311 +G (3df, 2pd) standard basis sets with the MP2 (FULL), MP4, MCSCF, MRSDCI, CCD and ST4CCD methods. In addition, vertical excited energies and oscillator strengths of the electronicstate (X1∑+ ) for HeLi+ were obtained from the MCSCF mothod. The results show that thestability of HeLi+ (X1∑+ ) and HeLi+ (a3∑+ ) is higher than that of HeLi(X2()+ ) and HeLi(a4II)respectively. Between HeLi+ (X1∑+ ) and HLi(X1∑+) ,the stability of the latter was higher thanthe former. For HeLi+ (X1∑+) ,the transition from A1∑+ state to B1II state (3σ→1 ) has larger oscillator values and smaller vertical transition energy.

关 键 词：元素簇合物 稳定性 氦 锂 簇合物 

分 类 号：O613.11[理学—无机化学] O614.111[理学—化学]