ZnS分子激发态光谱性质的理论研究

Theoretical study on spectroscopic properties of excited states of ZnO molecule

采用考虑了戴维森修正的多参考组态相互作用(MRCI+Q)方法计算了ZnS分子能量最低的四条解离极限相关的18个Λ-S态的电子结构,并给出了势能曲线(PECs).计算中纳入了相对论效应和Zn原子3d轨道的芯-价电子关联效应.通过求解一维径向Schr?dinger方程,拟合出了一些典型束缚态的光谱常数,与之前的实验数据符合得很好.还计算了ZnS分子的永久偶极矩(PDMs),通过对PDMs的分析,阐明了ZnS分子中Zn原子与S原子的成键特性与分子极性.借助耦合矩阵元说明了电子态之间的扰动作用和预解离机制.最后,计算了^(1)Σ^(+)-^(1)Σ^(+)和^(1)Π-^(1)Σ^(+)态的跃迁偶极矩(TDMs)、Franck-Condon因子(FCFs)和振动能级信息以及自发辐射寿命.

The electronic structures of 18Λ-S states,which are related to the four lowest dissociation limits of ZnS molecular energy,have been calculated using the Davidson correction multi-reference configuration interaction(MRCI+Q)method,and the potential energy curves(PECs)have been provided.The calculation also takes into account the relativistic effect and core-valence electron correlation effect of 3d orbit of Zn atom.By solving the one-dimensional radial Schrodinger equation,fit the spectral constants of some typical bound states,which are in good agreement with previous experimental data.The permanent dipole moment(PDMs)of the ZnS molecule is also calculated.By analyzing the PDMs,the bonding characteristics and molecular polarity of Zn and S atoms in the ZnS molecule are clarified.Elucidate perturbations between electron states and mechanisms of predissociation by coupling matrix elements.Finally,the transition dipole moments of ^(1)Σ^(+)-^(1)Σ^(+) and ^(1)Π-^(1)Σ^(+) Sstates,as well as the Franck-Condon factor,vibration-level information,and spontaneous radiative lifetime are calculated.