On polarization functions for Gaussian basis sets.

Area of Science:

• Computational chemistry
• Quantum chemistry
• Theoretical chemistry

Background:

• Gaussian basis sets are crucial for accurate quantum chemical calculations.
• Optimization of polarization functions can be computationally expensive and time-consuming.
• A need exists for efficient methods to generate and utilize polarization functions.

Purpose of the Study:

• To introduce a novel technique for selecting polarization functions directly from Gaussian exponents.
• To demonstrate the applicability and accuracy of the proposed method using various basis sets.
• To provide a computationally efficient alternative for generating polarized basis sets.

Main Methods:

• Developed a technique to derive polarization functions from primitive Gaussian exponents.
• Applied the method initially to Polynomial Generator Coordinate Hartree-Fock (PGCHF) generated basis sets.
• Extended the technique to standard basis sets like cc-pVQZ and pc-3.

Main Results:

• Calculated total electronic energies, equilibrium geometries, and vibrational frequencies for molecules (H to Ba).
• Demonstrated the effectiveness of the new polarized basis sets derived from the technique.
• Showcased the technique's ability to transfer polarization functions between different basis sets.

Conclusions:

• The presented technique offers a direct and efficient way to incorporate polarization functions.
• This method is versatile and applicable to various flexible Gaussian basis sets.
• The approach simplifies the generation of accurate polarized basis sets for computational chemistry.