A reduced-cost two-component relativistic equation-of-motion coupled cluster method for the double electron attachment problem

Abstract

We present a computationally efficient relativistic formulation of the equation-of-motion coupled-cluster (EOM-CC) method for the double electron attachment (DEA) problem. In this work, the exact two-component Hamiltonian within the atomic mean-field approximation is employed, yielding results that are in close agreement with the corresponding four-component calculations. However, canonical DEA-EOM-CCSD calculations become prohibitively expensive for heavy elements and large basis sets due to the substantial memory requirements associated with the complex-valued 3p1h excitation manifold. To address this limitation, we introduce a new state-specific frozen natural spinor basis that significantly reduces the virtual space through two controllable truncation thresholds. Furthermore, the use of Cholesky decomposition for the two-electron integrals provides an additional reduction in memory requirements. The performance of the proposed approach is demonstrated through calculations of double ionization potentials and excitation energies for group-12 and group-14 heavy elements. Vertical excitation energies for heavy chalcogen dimers are also presented. In addition, a range of diatomic spectroscopic constants is evaluated for group-13 hydrides. Finally, the method is applied to predict the singlet-triplet gaps of dihalocarbenes, indicating that an accurate description of these systems may require excitation manifolds beyond the 3p1h space.