Relativistic Real-Time Time-Dependent Equation-of-Motion Coupled-Cluster.

We present a relativistic time-dependent equation-of-motion coupled-cluster with single and double excitations (TD-EOM-CCSD) formalism. Unlike other explicitly time-dependent quantum chemical methods, the present approach considers the time correlation function of the dipole operator, as opposed to the expectation value of the time-dependent dipole moment. We include both scalar relativistic effects and spin-orbit coupling variationally in this scheme via the use of the exact two-component (X2C) wave function as the reference that enters the coupled-cluster formalism. In order to evaluate the accuracy of X2C-TD-EOM-CCSD, we compare zero-field splitting in atomic absorption spectra of open-shell systems (Na, K, Mg+, and Ca+) with values obtained from experiment. In closed-shell species (Na+, K+, Mg2+, and Ca2+), we observe singlet-triplet mixing in the X2C-TD-EOM-CC calculations, which results from the use of the X2C reference. The effects of the X2C reference are evaluated by comparing spectra derived from X2C-TD-EOM-CC calculations to those from TD-EOM-CC calculations using a complex generalized Hartree-Fock ([Formula: see text]-GHF) reference.