Application of numerical basis sets to hydrogen bonded systems: a density functional theory study

Area of Science:

• Computational chemistry
• Quantum chemistry
• Molecular modeling

Background:

• Accurate description of hydrogen-bonded systems is crucial in chemistry and biology.
• Gaussian-type basis sets are widely used but can be computationally expensive.
• Numerical basis sets offer an alternative approach for electronic structure calculations.

Purpose of the Study:

• To compare the accuracy of numerical and Gaussian-type basis sets for hydrogen-bonded systems.
• To evaluate the performance of these basis sets in predicting geometries and binding energies.
• To assess the computational efficiency of numerical basis sets for large molecular systems.

Main Methods:

• Investigated hydrogen-bonded systems using both numerical and Gaussian-type basis sets.
• Calculated and compared geometric parameters and binding energies.
• Performed geometry optimization for phosphinic acid dimer to assess computational time.

Main Results:

• Numerical basis sets yielded accurate geometric parameters for hydrogen-bonded systems.
• A tendency for numerical basis sets to overestimate binding energies was observed.
• Geometry optimization of phosphinic acid dimer was significantly faster with numerical basis sets.

Conclusions:

• Numerical basis sets provide accurate geometries for hydrogen-bonded systems.
• While binding energies may be overestimated, numerical basis sets show computational advantages for large system optimizations.
• Numerical basis sets are a promising tool for computational chemistry, particularly in large-scale molecular modeling.