How well do static electronic dipole polarizabilities from gas-phase experiments compare with density functional and...

Area of Science:

• Computational Chemistry
• Quantum Chemistry
• Molecular Modeling

Background:

• Static electronic dipole polarizability is a crucial molecular property.
• Accurate prediction of polarizability is essential for understanding molecular interactions and responses to electric fields.
• Previous computational methods have varying degrees of accuracy.

Purpose of the Study:

• To calculate static electronic dipole polarizabilities for a large set of 135 molecules.
• To evaluate the performance of recently recommended density functionals and second-order Møller-Plesset perturbation theory for polarizability calculations.
• To compare computational results with the best available gas-phase experimental data.

Main Methods:

• Utilized second-order Møller-Plesset perturbation theory (MP2).
• Employed six recently recommended density functionals for polarizability calculations.
• Compared calculated polarizabilities against experimental gas-phase data for 135 molecules.

Main Results:

• The LC-τHCTH and M11 functionals achieved the lowest mean absolute percent deviations (3.03% and 3.08%) from experimental values for all 135 molecules.
• Excluding eight potential outliers, the deviations decreased to 2.42% and 2.48% for LC-τHCTH and M11, respectively.
• Identified 32 molecules where calculated and experimental values show significant discrepancies, suggesting further investigation.

Conclusions:

• LC-τHCTH and M11 functionals demonstrate high accuracy for calculating static electronic dipole polarizabilities.
• The study provides a reliable benchmark for computational polarizability predictions.
• Discrepancies in specific cases highlight areas for future experimental and theoretical refinement.