TlCl^(+)的光谱性质和跃迁性质

Spectroscopic and Transition Properties of TlCl^(+)

采用多组态相互作用方法计算TlCl^(+)前两个离解极限所对应的14个L-S态(X^(2)Π,A^(2)S^(+),B^(2)S^(+),14S^(+),2^(2)Π,14D,14S-,1^(2)D,1^(2)S-,3^(2)S^(+),14Π,3^(2)Π,^(2)4Π,^(2)4S^(+))的势能曲线和跃迁偶极矩,结果表明:TlCl^(+)的X^(2)Π和A^(2)S^(+)态都为弱束缚态,且两个态的能级非常接近;3^(2)Π态具有双势阱结构,^(2)4Π和^(2)4S^(+)态为排斥态.通过求解薛定谔方程得到束缚态的光谱常数,以及A^(2)Σ^(+)→X^(2)Π、B^(2)Σ^(+)→X^(2)Π、3^(2)Σ^(+)→X^(2)Π、^(2)^(2)Π→X^(2)Π和1^(2)Δ→X^(2)Π跃迁的弗兰克-康登因子和自发辐射速率,其中3^(2)Σ^(+)→X^(2)Π跃迁的自发辐射速率最大,达到了1.83^(2)×10^(5)s^(-1),3^(2)Σ^(+)的自发辐射寿命为5.46 ms.

The potential energy curves and transition dipole moments of fourteen L-S states(X^(2)Π,A^(2)S^(+),B^(2)S^(+),14S^(+),2^(2)Π,14D,14S-,1^(2)D,1^(2)S-,3^(2)S^(+),14Π,3^(2)Π,^(2)4Π,^(2)4S^(+))correlating with two lowest dissociation channels of TlCl^(+)were performed using multi-reference configuration interaction method.The results indicate that the X^(2)Πand A^(2)S^(+)are both weakly bound states,the energy difference between these two states is closed.The 3^(2)Πstate exhibits a double-well,while the^(2)4Πand^(2)4S^(+)are both repul-sive states.The spectroscopic constants of bound states and Franck-Condon factors,spontaneous radiative rates of the A^(2)Σ^(+)→X^(2)Π,B^(2)Σ^(+)→X^(2)Π,3^(2)Σ^(+)→X^(2)Π,^(2)^(2)Π→X^(2)Π,1^(2)Δ→X^(2)Πtransitions are obtained by solving the Schrödinger equation.The radiative rate of the 3^(2)Σ^(+)→X^(2)Πtransition is the largest,which is 1.83^(2)×10^(5)s^(-1),and the spontaneous radiative lifetime of the 3^(2)Σ^(+)state is 5.46 ms.