Computational methods for investigating organic radical species.

Area of Science:

• Computational chemistry
• Quantum chemistry
• Organic radical chemistry

Background:

• Computational analysis of organic radicals is complex.
• Accurate prediction of radical properties is crucial for various chemical applications.
• Existing methods require rigorous evaluation for reliability.

Purpose of the Study:

• To compare the performance of various Density Functional Theory (DFT) and wavefunction methods.
• To assess the accuracy of these methods in predicting key organic radical properties.
• To identify the most reliable computational approaches for studying organic radicals.

Main Methods:

• Utilized a range of DFT functionals, including hybrid meta-GGA and range-separated hybrids.
• Employed various basis sets such as 6-311G**, cc-pVTZ, and def2-TZVP.
• Calculated radical stabilization energies, bond dissociation energies, and redox potentials.

Main Results:

• The hybrid meta-GGA functional M062X-D3(0) showed high accuracy.
• Range-separated hybrid functionals ωB97M-V and ωB97M-D3(BJ) also demonstrated reliable performance.
• Consistent accuracy was observed across different tested basis sets.

Conclusions:

• M062X-D3(0), ωB97M-V, and ωB97M-D3(BJ) are recommended for computational studies of organic radicals.
• These functionals provide accurate predictions of radical properties, aiding future research.
• The choice of method and basis set significantly impacts the reliability of organic radical computations.