An explicitly-correlated method of calculation of excited states with spin-orbit couplings, has been formulated and implemented. Developed approach utilizes left and right eigenvectors of equation-of-motion coupled-cluster model, which is based on the linearly approximated explicitly correlated coupled-cluster singles and doubles [CCSD(F12)] method. The spin-orbit interactions are introduced by using the spin-orbit mean field (SOMF) approximation of the Breit-Pauli Hamiltonian. Numerical tests for several atoms and molecules show good agreement between explicitly-correlated results and the corresponding values, calculated in complete basis set limit (CBS); the highly-accurate excitation energies can be obtained already at triple-ζ$\zeta$ level.

已经制定并实现了一种显式相关的具有自旋轨道耦合的激发态计算方法。所开发的方法利用运动方程耦合集群模型的左右特征向量，该模型基于线性近似显式相关耦合集群单打和双打[CCSD（F12）]方法。通过使用Breit-Pauli Hamiltonian的自旋轨道平均场（SOMF）逼近来引入自旋轨道相互作用。对几个原子和分子的数值测试表明，显式关联的结果与以完整基准集限制（CBS）计算的相应值之间具有很好的一致性；可以在三倍ζ处获得高精度的激发能$\zeta$ 等级。