Static dipole polarizabilities of polyacenes using self-interaction-corrected density functional approximations

Area of Science:

• Computational Chemistry
• Quantum Chemistry
• Materials Science

Background:

• Density functional approximations (DFAs) commonly overestimate polarizabilities in chain-like molecules.
• Accurate calculation of molecular properties like polarizability and ionization potential is crucial for understanding material behavior.

Purpose of the Study:

• To investigate static electric dipole polarizabilities and vertical ionization potentials of polyacenes.
• To evaluate the effectiveness of the Fermi-Löwdin orbital-based self-interaction corrected (FLOSIC) and locally scaled self-interaction correction (LSIC) methods for these properties.

Main Methods:

• Employed the Fermi-Löwdin orbital-based self-interaction corrected (FLOSIC) density functional method.
• Applied the recently developed locally scaled self-interaction correction (LSIC) method.
• Calculated static electric dipole polarizabilities and vertical ionization potentials for polyacenes (benzene to pentacene).

Main Results:

• FLOSIC-DFA showed an overcorrection tendency for molecular polarizabilities.
• LSIC effectively corrected the overcorrection, yielding results in excellent agreement with coupled-cluster single and double (CCSD) reference values.
• LSIC also provided good agreement for vertical ionization potentials with experimental data.

Conclusions:

• The LSIC method offers a significant improvement over standard DFAs and FLOSIC for calculating polyacene polarizabilities.
• LSIC demonstrates high accuracy for both polarizabilities and ionization potentials, making it a reliable computational tool.
• This work validates LSIC as a robust method for electronic property calculations in conjugated organic molecules.