2026-10-13T12:01:34Z https://api.figshare.com/v2/oai

oai:figshare.com:article/33954555 2026-09-21T13:45:14Z category_1 category_915 category_21 category_873 category_64 portal_63 item_type_3 month_year_09_2026

Dielectric-Screened Functionals for Cis–Trans Excitation Energies of Solvated Azobenzene Derivatives: Screening Trends in Comparison with Experiment and Published GW/BSE Calculations Aswathy Jayachandran (25083765) Barry D. Dunietz (1287738) Biophysics Physical Sciences not elsewhere classified Biotechnology Chemical Sciences not elsewhere classified Cancer solvated azobenzene derivatives prototypical molecular photoswitch previously reported high polarizable continuum model photoactive molecular systems obtain excited states electronically excited states framework employs dielectric phase excitation energies functionals within pcm environmental dielectric screening environmental screening screened functionals dielectric screening environmental effects screening trends range screening state properties separated hybrid screened range reliable treatment rational design offering insights nuclear polarization nuclear contributions findings demonstrate field approach field alternative effective description define long cost wavefunction based approaches also accounts 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. 2026-09-21T00:00:00Z Dataset Dataset 10.1021/acs.jctc.6c01302.s002 https://figshare.com/articles/dataset/Dielectric-Screened_Functionals_for_Cis_Trans_Excitation_Energies_of_Solvated_Azobenzene_Derivatives_Screening_Trends_in_Comparison_with_Experiment_and_Published_GW_BSE_Calculations/33954555 CC BY-NC 4.0