Near and vacuum UV polarization spectroscopy of 1,4-distyrylbenzene

Nguyen, Duy Duc; Jones, Nykola C.; Hoffmann, S. V.; Spanget‐Larsen, Jens

doi:10.1016/j.saa.2022.122019

Cited by 3 publications

References 45 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

Explicit Modelling of Spectral Bandshapes by a Mixed Quantum‐Classical Approach: Solvent Order and Temperature Effects in the Optical Spectra of Distyrylbenzene

Cerezo,

Gierschner,

Santoro

et al. 2024

ChemPhysChem

View full text Add to dashboard Cite

The absorption and emission spectral shapes of a flexible organic probe, the distyrylbenzene (DSB) dye, are simulated accounting for the effect of different environments of increasing complexity, ranging from a homogeneous, low‐molecular‐weight solvent, to a long‐chain alkane, and, eventually, a channel‐forming organic matrix. Each embedding is treated explicitly, adopting a mixed quantum‐classical approach, the Adiabatic Molecular Dynamics ‐‐ generalized vertical Hessian (Ad‐MD|gVH) model, which allows a direct simulation of the environment‐induced constraining effects on the vibronic spectral shapes. In such a theoretical framework, the stiff modes of the dye are described at a quantum level within the harmonic approximation, including Duschinsky mixing effects, while flexible degrees of freedom of the solute (e.g. torsions) and those of the solvent are treated classically by means of molecular dynamics sampling. Such a setup is shown to reproduce the distinct effects exerted by the different environments in varied thermodynamic conditions. Besides allowing for a first‐principles rationale on the supramolecular mechanism leading to the experimental spectral features, this result represents the first successful application of the Ad‐MD|gVH method to complex embeddings and supports its potential application to other heterogeneous environments, such as for instance pigment‐protein complexes or organic dyes adsorbed into metal‐organic frameworks.

show abstract