GeCl分子激发态的势能曲线和辐射寿命的理论研究

Theoretical investigations on the potential energy curve and radiation lifetimes of the excited states of GeCl molecule

采用考虑Davidson校正、标量相对论效应、芯-价电子关联和自旋-轨道耦合效应高精度的多参考组态相互作用方法计算了GeCl分子的最低解离极限Ge(3Pg)+Cl(2Pu)对应的12个Λ-S电子态的势能曲线.基于计算得到的势能曲线,求解一维核运动的Sch?rdinger方程得出束缚态的光谱常数,这些光谱常数与实验值符合较好.本文计算了12个Λ-S态的电偶极矩随核间距的变化,分析了电子态组态成分的变化对电偶极矩的影响.本文还研究了GeCl分子的辐射跃迁性质,给出了激发态到基态之间和低激发态之间的跃迁偶极矩和电子态之间的Franck-Condon因子,并根据计算得到的跃迁偶极矩和Franck-Condon因子计算出了束缚激发态低振动能级的辐射寿命.

The potential energy curves of 12Λ-S states corresponding to the lowest dissociation limit Ge(3Pg)+Cl(2Pu)of GeCl are calculated by using the high precision multireference configuration interaction(MRCI)method.Davidson correction,scalar relativistic effect,core-valence electron correlation and spin-orbit coupling effect are considered in the calculations.Based on the calculated potential energy curves(PECs),the spectroscopic constants of the bound states are evaluated,which are in good agreement with the experimental values.We calculate the dipole moment of the 12Λ-S states at different internuclear distances,and analyze the influence of the change of electronic configurations on the dipole moments.We also investigate the radiative transition properties of GeCl,and obtain the transition dipole moments(TDMs)from excited states to ground state and from excited states to lower excited states,and determine the Franck-Condon factors(FCFs)between these states.Finally,the radiative lifetimes of low vibrational energy level of bound excited states are evaluated by the computed TDMs and FCFs.