从耦合团簇二次响应函数的厄米特公式计算电子激发态之间的跃迁矩
Transition moments between excited electronic states from the Hermitian formulation of the coupled cluster quadratic response function
摘要：
本文介绍了一种基于耦合集团理论[B]的期望值形式计算激发态间跃迁矩的新方法。Jeziorski和R. Moszynski，Int. J. Quant. 48，161（1993）]。新方法的工作表达式只采用耦合的集群振幅。在本论文中采用的近似的集群扩展是有限的单，双，和线性三重激发。计算得到的碱土原子单重态-单重态和三重态-三重态跃迁的偶极跃迁几率与已有的理论和实验数据符合得很好。与现有的耦合团簇响应理论相比，即使截断团簇算符中的激发，通过使用我们的方法获得的矩阵元也满足Hermitian对称性。作为新方法的数值证据的一部分，我们报告的激发三重态之间的过渡时刻，尚未在文献中报道的耦合簇理论的计算。在我们的计算中使用了根据相关一致性原理构造的Slater型基组。
英文摘要：
We introduce a new method for the computation of the transition moments between the excited electronic states based on the expectation value formalism of the coupled cluster theory [B. Jeziorski and R. Moszynski, Int. J. Quant. Chem. 48, 161 (1993)]. The working expressions of the new method solely employ the coupled cluster amplitudes. In the approximation adopted in the present paper the cluster expansion is limited to single, double, and linear triple excitations. The computed dipole transition probabilities for the singlet-singlet and triplet-triplet transitions in alkali earth atoms agree well with the available theoretical and experimental data. In contrast to the existing coupled cluster response theory, the matrix elements obtained by using our approach satisfy the Hermitian symmetry even if the excitations in the cluster operator are truncated. As a part of the numerical evidence for the new method, we report calculations of the transition moments between the excited triplet states which have not yet been reported in the literature within the coupled cluster theory. Slater-type basis sets constructed according to the correlation-consistency principle are used in our calculations.
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