Time-Dependent Density-Functional Theory for Modeling Solid-State Fluorescence Emission of Organic Multicomponent...

Area of Science:

• Computational Chemistry
• Materials Science
• Solid-State Physics

Background:

• Accurate modeling of solid-state fluorescence is crucial for designing new organic luminescent materials.
• Existing methods may lack the precision needed to capture subtle effects of crystal packing and intermolecular interactions.
• Time-dependent density-functional theory (TD-DFT) offers a promising avenue for such calculations.

Purpose of the Study:

• To present and validate a computational approach for modeling solid-state fluorescence spectra of organic crystalline materials.
• To assess the accuracy of time-dependent density-functional theory (TD-DFT) calculations for predicting emission spectra.
• To explore the potential for in silico design of organic luminescent materials.

Main Methods:

• Utilized the plane-wave/pseudopotential code CASTEP for TD-DFT calculations.
• Modeled solid-state fluorescence spectra of various organic cocrystals.
• Compared computational results with experimental emission spectra.

Main Results:

• The computational method demonstrated good to excellent agreement with experimental data across a range of emission wavelengths.
• Calculated spectra accurately reproduced experimental observations for the tested organic cocrystals.
• The approach successfully captured the influence of intermolecular interactions and crystal packing on luminescence.

Conclusions:

• The developed TD-DFT approach provides a reliable tool for modeling solid-state fluorescence spectra of organic materials.
• This method offers valuable insights into structure-property relationships governing organic luminescence.
• Enables the rational, in silico design and discovery of novel organic luminescent materials with tailored properties.