AgO分子激发态光谱性质的理论研究

Theoretical study on spectral properties of AgO molecular excited states

使用高精度多参考组态相互作用(MRCI)方法,计算了AgO分子能量最低的3条解离极限的全部19个Λ-S态的能量.计算过程中考虑了戴维森校正、芯-价电子关联效应以及自旋轨道耦合效应.根据计算结果绘制了AgO分子的势能曲线(PECs),并求解一维核运动的Sch?rdinger方程得到束缚态的光谱常数,计算结果与实验结果吻合较好.计算了17个Λ-S态的电偶极矩(DMs)随着核间距的变化规律.借助于1^(2)Σ^(+)与1^(2)Σ^(-),22Π,1^(4)Σ^(-),1^(4)Π态之间的自旋轨道耦合矩阵元的绝对值对1^(2)Σ^(+)态的扰动进行讨论.计算AgO分子低激发态之间的跃迁性质,包括跃迁偶极矩(TDMs)和弗兰克-康登因子(FCFs)以及辐射寿命.

The energies of 19Λ-S states with the three lowest dissociation limits of AgO are calculated by using the high-level MRCI method.Davidson correction,core-valence electron correlation effect and spin-orbit coupling effect are considered in the calculation.According to the calculated results,the potential energy curves(PECs)of AgO are plotted,and the spectroscopic constants of bound states are obtained by solving the Sch?rdinger equation of one-dimensional nuclear motion.The calculated results are in good agreement with the experimental results.The variation of the electric dipole moments(DMs)of 17Λ-S states with the internuclear distance is calculated.The perturbation of the1^(2)Σ^(+)state is discussed by means of the absolute values of the spin-orbit coupling matrix elements of 1^(2)Σ^(+)-1^(2)Σ^(-),1^(2)Σ^(+)-2~2Π,1^(2)Σ^(+)-1^(4)Σ^(-)and1^(2)Σ^(+)-1^(4)Π.The transition properties between low excited states of AgO are calculated,including transition dipole moments(TDMs),Frank-Condon factors(FCFs)and radiation lifetimes.