Frequency-Dependent Quadratic Response Properties and Two-Photon Absorption from Relativistic Equation-of-Motion...

We present the implementation of quadratic response theory based upon the relativistic equation-of-motion coupled cluster method. We showcase our implementation, whose generality allows us to consider both time-dependent and time-independent electric and magnetic perturbations, by considering the static and frequency-dependent hyperpolarizability of hydrogen halides (HX, X = F-At), providing comprehensive insights into their electronic response characteristics. Additionally, we evaluated the Verdet constant for noble gases Xe and Rn and discussed the relative importance of relativistic and electron correlation effects for these magneto-optical properties. Finally, we calculate the two-photon absorption cross sections of transition [ns¹S₀ → (n + 1)s¹S₀] of Ga⁺ and In⁺, which are suggested as candidates for new ion clocks. As our implementation allows for the use of nonrelativistic Hamiltonians as well, we have compared our EOM-QRCC results to the QR-CC implementation in the DALTON code and show that the differences between CC and EOMCC response are in general smaller than 5% for the properties considered. Collectively, the results underscore the versatility of our implementation and its potential as a benchmark tool for other approximated models, such as density functional theory for higher-order properties.