Communication: one third: a new recipe for the PBE0 paradigm

Area of Science:

• Computational chemistry
• Quantum chemistry
• Materials science

Background:

• The PBE0 hybrid functional is widely used in computational chemistry.
• Accurate prediction of molecular properties requires precise density functional approximations.

Purpose of the Study:

• To evaluate the performance of the parameter-free PBE0-1/3 hybrid functional.
• To compare PBE0-1/3 against the established PBE0 functional for various chemical properties.

Main Methods:

• Utilizing the PBE0-1/3 functional, which combines the PBE functional with 1/3 exact exchange.
• Assessing performance across datasets including G2-148 (atomization energies), NCB31 (weak interactions), and HB10 (hydrogen bonding).
• Calculating vertical excitation energies.

Main Results:

• PBE0-1/3 demonstrates enhanced accuracy for atomization energies, weak interactions, and hydrogen bonding compared to PBE0.
• The functional also shows improved performance for vertical excitation energies.
• Numerical results confirm the increased predictive power of PBE0-1/3.

Conclusions:

• The parameter-free PBE0-1/3 functional offers superior performance over PBE0 for a range of chemical properties.
• A mixing coefficient of one third is proposed for PBE-based hybrid functionals.