First-principles calculation of local atomic polarizabilities

Area of Science:

• Computational Chemistry
• Quantum Chemistry
• Theoretical Chemistry

Background:

• Traditional methods for atomic polarizability determination often include nonlocal effects like charge polarization, limiting their accuracy.
• Accurate calculation of atomic polarizabilities is crucial for understanding molecular interactions and predicting chemical properties.

Purpose of the Study:

• To introduce a novel, fully ab initio method for calculating localized atomic polarizabilities.
• To assess the accuracy and practical utility of these localized polarizabilities in calculating induction energies.

Main Methods:

• Calculating the response of atomic multipoles to a local electrostatic potential to derive localized atomic polarizabilities.
• Comparing calculated induction energies using localized polarizabilities against established ab initio induction energies.
• Investigating the transferability of localized polarizabilities within the alkane series.

Main Results:

• The new method provides fully ab initio localized atomic polarizabilities, overcoming limitations of nonlocal effects.
• Calculated induction energies using localized polarizabilities demonstrate improved absolute accuracy.
• The multipolar induction series shows better convergence with localized polarizabilities compared to molecular ones.
• Localized polarizabilities exhibit good transferability in alkanes.

Conclusions:

• The developed method offers a more accurate and reliable approach to determining atomic polarizabilities.
• Localized atomic polarizabilities are advantageous for calculating induction energies, enhancing computational chemistry applications.
• This method represents a significant advancement in the theoretical treatment of atomic and molecular properties.