Reduced Serially Improved GTOs for Molecular Applications from H to Ar: Efficient Diffuse Functions in Augmented...

Area of Science:

• Computational Chemistry
• Quantum Chemistry
• Theoretical Chemistry

Background:

• Basis sets are crucial for accurate quantum chemical calculations.
• Existing basis sets like Dunning's have limitations in handling large systems and avoiding linear dependencies.
• Development of efficient and robust basis sets is an ongoing need in computational chemistry.

Purpose of the Study:

• To introduce a new family of Gaussian-type orbital basis sets, Serially Improved Gaussian-type Orbitals for Molecular Applications (SIGMA).
• To develop both standard and augmented versions of the SIGMA basis sets for elements hydrogen to argon.
• To demonstrate the improved performance and robustness of the augmented reduced SIGMA basis sets.

Main Methods:

• Development of a new SIGMA basis set with fewer primitive functions and no shared exponents.
• Creation of an augmented version (reduced SIGMA) with contracted diffuse functions.
• Performance evaluation through atomic and molecular calculations at various computational levels.

Main Results:

• The reduced SIGMA basis sets exhibit fewer linear dependencies, leading to better convergence in minimization processes.
• Augmented reduced SIGMA basis sets show improved performance compared to Dunning and other common basis sets.
• Demonstrated positive impact on energy optimization procedures in computational chemistry.

Conclusions:

• The novel SIGMA basis set family provides a more efficient and reliable alternative for quantum chemical calculations.
• The augmented reduced SIGMA sets are particularly advantageous for large and compact systems.
• This development advances the accuracy and efficiency of computational chemistry methods.