Rational Density Functional Selection Using Game Theory.

Area of Science:

• Computational chemistry
• Theoretical chemistry
• Quantum chemistry

Background:

• The selection of density functionals and basis sets in theoretical chemistry is often subjective, relying on user expertise.
• This leads to a 'paradox of choice' with numerous available computational chemistry tools.
• Existing methods lack objective criteria for functional and basis set selection.

Purpose of the Study:

• To develop an objective methodology for selecting density functionals and basis sets.
• To circumvent the traditional user-centric and subjective selection process.
• To provide a mathematically justified approach for computational chemistry tool selection.

Main Methods:

• Application of game theory to identify optimal functional/basis set combinations.
• Devising a three-player game involving accuracy, complexity, and similarity.
• Utilizing Nash equilibrium solutions to determine optimal selections.

Main Results:

• A novel, objective method for selecting density functionals and basis sets was developed.
• The game theory approach provides a deterministic and mathematically justified selection procedure.
• The methodology allows for systematic improvement of results by expanding the knowledge base.

Conclusions:

• The game theory framework offers an objective alternative to subjective selection of computational chemistry parameters.
• This approach enhances the reliability and reproducibility of theoretical chemistry calculations.
• The method provides a clear, mathematical basis for choosing density functionals and basis sets.