Department of Chemistry, Physical Chemistry Section, Jadavpur University, Kolkata 700 032, India.
J Phys Chem A. 2009 Sep 17;113(37):10089-95. doi: 10.1021/jp904416w.
Electronic structure and spectroscopic properties of the ground and low-lying excited states of GeSi+ have been studied by using multireference singles and doubles configuration interaction (MRDCI) method that includes relativistic effective core potentials of Ge and Si atoms. At least 17 Lambda-Sigma bound states of GeSi+ are reported within 5 eV. Potential energy curves of 24 Lambda-Sigma states which correlate with the lowest two dissociation limits, Ge+(2Pu)+Si(3Pg) and Ge(3Pg)+Si+ (2Pu) are constructed. The ground-state dissociation energy of GeSi+ is estimated to be 3.116 eV. The spin-orbit coupling among all states correlating the two dissociation limits is also included in the calculations. Spectroscopic constants of 27 Omega states of the ion are reported. Effects of the spin-orbit coupling on the spectroscopic properties are also studied. Potential energy curves of Omega states show several avoided crossings. Transition probabilities of many electric dipole allowed and spin-forbidden transitions are computed. Transitions such as 24Sigma(-)-X4Sigma- and 44Sigma(-)-X4Sigma- are found to be highly probable. Partial lifetimes for some weak spin-forbidden transitions to the ground-state components, X4Sigma(1/2)- and X4Sigma(3/2)- are also computed.
我们采用包含锗和硅原子相对论有效核势的多参考态单双组态相互作用（MRDCI）方法研究了 GeSi+的基态和低激发态的电子结构和光谱性质。在 5 eV 内报告了 GeSi+的至少 17 个 Lambda-Sigma 束缚态。构建了与最低两个离解极限 Ge+(2Pu)+Si(3Pg)和 Ge(3Pg)+Si+(2Pu)相关的 24 个 Lambda-Sigma 态的势能曲线。GeSi+的基态离解能估计为 3.116 eV。计算中还包括所有与两个离解极限相关联的态之间的自旋轨道耦合。报告了离子 27 Omega 态的光谱常数。还研究了自旋轨道耦合对光谱性质的影响。Omega 态的势能曲线显示了几个避免交叉。计算了许多电偶极允许和自旋禁戒跃迁的跃迁概率。发现 24Sigma(-)-X4Sigma-和 44Sigma(-)-X4Sigma-等跃迁很可能发生。还计算了一些弱自旋禁戒跃迁到基态分量 X4Sigma(1/2)-和 X4Sigma(3/2)-的部分寿命。
