Spin-scaled double hybrids with long-range correction solve the TD-DFT overestimation problem in BODIPY dyes:...

Area of Science:

• Computational Chemistry
• Quantum Chemistry
• Materials Science

Background:

• Time-dependent density functional theory (TD-DFT) methods commonly overestimate electronic excitation energies for boron-dipyrromethene (BODIPY) dyes.
• Accurate prediction of absorption energies is crucial for designing novel BODIPY dyes with specific optical properties.

Purpose of the Study:

• To establish a benchmark dataset (SBYD31) for BODIPY absorption energies.
• To evaluate the performance of 28 different TD-DFT methods, including novel spin-scaled double hybrids, for BODIPY dyes.
• To identify accurate and reliable TD-DFT methods for predicting BODIPY dye properties.

Main Methods:

• Development and utilization of the SBYD31 benchmark set for BODIPY absorption energies.
• Systematic assessment of 28 TD-DFT methods, focusing on spin-scaled double hybrids with long-range correction.
• Experimental validation of the top-performing computational methods using newly synthesized BODIPY dyes.

Main Results:

• Spin-scaled double hybrid functionals with long-range correction significantly reduce the overestimation of excitation energies in BODIPY dyes.
• The developed methods achieve chemical accuracy (within 0.1 eV) for BODIPY absorption energies, surpassing previous TD-DFT approaches.
• Three recommended methods (SOS-ωB2GP-PLYP, SCS-ωB2GP-PLYP, SOS-ωB88PP86) demonstrated high accuracy, confirmed by experimental measurements.

Conclusions:

• Time-dependent double hybrids with spin-component scaling and long-range correction are highly effective for accurately calculating BODIPY dye absorption energies.
• This study provides the most accurate TD-DFT absorption energies for BODIPY dyes reported to date.
• The findings will aid in the rational design and development of advanced BODIPY-based materials.