Ab Initio Investigation of Excited States and Absorption Spectra of Small Mercury Clusters (Hg2−5)
Abstract
We report a systematic \textit{ab initio} investigation of the excited states and absorption spectra of small mercury clusters (Hg2−5). 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 ±500 cm−1 of experiment, whereas MR-CISD deviates by about ±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 Hg3, Hg4, Hg5, 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.
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BibTeX
@misc{novotny2026initio,
title = {{Ab Initio Investigation of Excited States and Absorption Spectra of Small Mercury Clusters (Hg$_2-5$)}},
author = {Michal Novotný and František Karlický},
howpublished = {arXiv},
year = {2026},
month = oct,
doi = {10.48550/arxiv.2610.10900},
eprint = {2610.10900},
archivePrefix = {arXiv},
url = {https://arxiv.org/abs/2610.10900},
}
RIS
TY - UNPB
TI - Ab Initio Investigation of Excited States and Absorption Spectra of Small Mercury Clusters (Hg_2−5)
AU - Michal Novotný
AU - František Karlický
PY - 2026
DA - 2026/10/07
PB - arXiv
DO - 10.48550/arxiv.2610.10900
UR - https://arxiv.org/abs/2610.10900
AB - 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 ±500 cm^−1 of experiment, whereas MR-CISD deviates by about ±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.
ER -