Dielectric-Screened Functionals for Cis-Trans Excitation Energies of Solvated Azobenzene Derivatives: Screening Trends in Comparison with Experiment and Published GW/BSE Calculations.
- 1Kent State University , Department of Chemistry and Biochemistry, Kent, Ohio44242, United States.
Abstract
Accurate modeling of electronically excited states in solution is essential for the rational design of photoactive molecular systems, but requires a reliable treatment of environmental effects. We present a mean-field approach that combines density functional theory with a polarizable continuum model (PCM) to account for environmental dielectric screening, providing an efficient mean-field alternative to higher-cost wavefunction- or many-body-based approaches. The framework employs dielectric-screened range-separated hybrid (SRSH) functionals within PCM to obtain excited states of solvated azobenzene derivatives, a prototypical molecular photoswitch. SRSH-PCM excitation energies better reproduce experiment when the larger static dielectric constant, which also accounts for nuclear polarization, is used to define long-range screening. Using the smaller optical dielectric constant, which represents purely electronic polarization, SRSH-PCM energies align better with previously reported high-quality GW-Bethe-Salpeter equation (GW/BSE) energies [Kshirsagar et al., JCTC 2020]. Our findings demonstrate that mean-field SRSH-PCM provides an effective description of excited-state properties while offering insights into the role of environmental screening and, in particular, the importance of accounting for nuclear contributions to dielectric screening in many-body calculations of solution-phase excitation energies.
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BibTeX
@article{jayachandran2026dielectricscreened,
title = {{Dielectric-Screened Functionals for Cis-Trans Excitation Energies of Solvated Azobenzene Derivatives: Screening Trends in Comparison with Experiment and Published GW/BSE Calculations.}},
author = {Aswathy Jayachandran and Barry D Dunietz},
journal = {Journal of chemical theory and computation},
year = {2026},
month = oct,
doi = {10.1021/acs.jctc.6c01302},
url = {https://europepmc.org/article/MED/42917271},
note = {CC BY},
}
RIS
TY - JOUR
TI - Dielectric-Screened Functionals for Cis-Trans Excitation Energies of Solvated Azobenzene Derivatives: Screening Trends in Comparison with Experiment and Published GW/BSE Calculations.
AU - Aswathy Jayachandran
AU - Barry D Dunietz
PY - 2026
DA - 2026/10/01
JO - Journal of chemical theory and computation
DO - 10.1021/acs.jctc.6c01302
UR - https://europepmc.org/article/MED/42917271
AB - Accurate modeling of electronically excited states in solution is essential for the rational design of photoactive molecular systems, but requires a reliable treatment of environmental effects. We present a mean-field approach that combines density functional theory with a polarizable continuum model (PCM) to account for environmental dielectric screening, providing an efficient mean-field alternative to higher-cost wavefunction- or many-body-based approaches. The framework employs dielectric-screened range-separated hybrid (SRSH) functionals within PCM to obtain excited states of solvated azobenzene derivatives, a prototypical molecular photoswitch. SRSH-PCM excitation energies better reproduce experiment when the larger static dielectric constant, which also accounts for nuclear polarization, is used to define long-range screening. Using the smaller optical dielectric constant, which represents purely electronic polarization, SRSH-PCM energies align better with previously reported high-quality GW-Bethe-Salpeter equation (GW/BSE) energies [Kshirsagar et al., JCTC 2020]. Our findings demonstrate that mean-field SRSH-PCM provides an effective description of excited-state properties while offering insights into the role of environmental screening and, in particular, the importance of accounting for nuclear contributions to dielectric screening in many-body calculations of solution-phase excitation energies.
SN - 1549-9618
SN - 1549-9626
ER -