Ab Initio Investigation of Excited States and Absorption Spectra of Small Mercury Clusters (Hg${}_{2-5}$)

Abstract

We report a systematic \textit{ab initio} investigation of the excited states and absorption spectra of small mercury clusters (Hg${}_{2-5}$). Benchmarking multi-reference configuration interaction (MR-CISD) and equation-of-motion coupled-cluster (EOM-CCSD) methods shows that EOM-CCSD/aug-cc-PVTZ-PP reproduces atomic excitation energies within $\pm$500 cm${}^{-1}$ of experiment, whereas MR-CISD deviates by about $\pm$1100 cm${}^{-1}$. For the mercury dimer, EOM-CCSD potential energy curves yield absorption bands in excellent agreement with experimental transitions, while asymptotic excitation energies closely match atomic references. Extending this methodology, we present the first systematic \textit{ab initio} study of absorption spectra of Hg${}_3$, Hg${}_4$, Hg${}_5$, which display broad bands in the ranges of 37000-60000 cm${}^{-1}$. The consistent agreement with experimental benchmarks and diagnostics confirming single-reference character validates EOM-CCSD as a robust approach for describing excited states and optical spectra of mercury clusters.