Absorption and Emission Spectra in Aqueous Solution with Coupled-Cluster Accuracy
Abstract
Quantitative prediction of electronic spectra in water requires an accurate treatment of electronic excitation, nuclear structure, and state-specific solvation including effects from hydrogen bonding. Here, photoacids and photobases in aqueous solution are used as stringent test systems for statespecific embedded cluster reference interaction site model calculations combined with the iterative coupled cluster models CC2 and CC3. Wigner nuclear-ensemble and adiabatic Hessian Franck-Condon calculations reproduce absorption and emission band maxima on an absolute energy scale with typical errors of 0.1–0.2 eV without empirical shift or scaling corrections; the energies of resolved 0–0 transitions in photobases are even reproduced within a few hundredths of an eV. The simulations also resolve contributions from different excited states and changes in the emitting species. Derived excited-state acidity changes, ∆pK∗ a , show similar accuracy for photoacids and photobases, with residual errors governed by cancellation or accumulation between protonation states.
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BibTeX
@misc{sulzner2026absorption,
title = {{Absorption and Emission Spectra in Aqueous Solution with Coupled-Cluster Accuracy}},
author = {Niklas Sülzner and Ömer F. C. Tiska and Julia Haberhauer and Patrick Kibies and Stefan M. Kast and Christof Hättig and Christof Hattig},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15010317/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010317/v1},
note = {CC BY-NC-ND},
}
RIS
TY - UNPB
TI - Absorption and Emission Spectra in Aqueous Solution with Coupled-Cluster Accuracy
AU - Niklas Sülzner
AU - Ömer F. C. Tiska
AU - Julia Haberhauer
AU - Patrick Kibies
AU - Stefan M. Kast
AU - Christof Hättig
AU - Christof Hattig
PY - 2026
DA - 2026/10/12
PB - ChemRxiv
DO - 10.26434/chemrxiv.15010317/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010317/v1
AB - Quantitative prediction of electronic spectra in water requires an accurate treatment of electronic excitation, nuclear structure, and state-specific solvation including effects from hydrogen bonding. Here, photoacids and photobases in aqueous solution are used as stringent test systems for statespecific embedded cluster reference interaction site model calculations combined with the iterative coupled cluster models CC2 and CC3. Wigner nuclear-ensemble and adiabatic Hessian Franck-Condon calculations reproduce absorption and emission band maxima on an absolute energy scale with typical errors of 0.1–0.2 eV without empirical shift or scaling corrections; the energies of resolved 0–0 transitions in photobases are even reproduced within a few hundredths of an eV. The simulations also resolve contributions from different excited states and changes in the emitting species. Derived excited-state acidity changes, ∆pK∗ a , show similar accuracy for photoacids and photobases, with residual errors governed by cancellation or accumulation between protonation states.
ER -