Complex-scaled equation-of-motion coupled-cluster method with single and double substitutions for autoionizing excited states: Theory, implementation, and examples

K.B. Bravaya, D. Zuev, E. Epifanovsky, and A.I. Krylov
J. Chem. Phys. 138, 124106 (2013)

Theory and implementation of complex-scaled variant of equation-of-motion coupled-cluster method for excitation energies with single and double substitutions (EOM-EE-CCSD) is presented. The complex-scaling formalism extends the EOM-EE-CCSD model to resonance states, i.e., excited states that are metastable with respect to electron ejection. The method is applied to Feshbach resonances in two well-studied systems, He and H-. The dependence of the results on one-electron basis set is quantified and analyzed. Energy decomposition and wave function analysis reveals that the origin of the dependence is in electron correlation, which is essential for the lifetime of Feshbach resonances. It is found that one electron basis should be sufficiently flexible to describe radial and angular electron correlation in a balanced fashion and at different values of the scaling parameter, theta. Standard basis sets that are optimized for not-complex-scaled calculations (theta=0) are not sufficiently flexible to describe the theta-dependence of the wave functions even when heavily augmented by additional sets.

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