Correlation Consistent Basis Sets for Explicitly Correlated Theory: The Transition Metals.

Area of Science:

• Computational Chemistry
• Quantum Chemistry
• Materials Science

Background:

• Explicitly correlated (F12) methods significantly accelerate the convergence of calculations to the basis set limit.
• Basis sets for d-block elements in F12 calculations are crucial for accurate modeling of transition metal systems.
• Existing basis sets may not be optimally efficient for d-block elements in F12 calculations.

Purpose of the Study:

• To develop and present new correlation consistent basis sets specifically designed for explicitly correlated (F12) calculations of d-block elements.
• To evaluate the performance of these new basis sets on benchmark datasets relevant to catalysis and metal clusters.
• To compare the accuracy and efficiency of the new basis sets against established combinations of basis sets.

Main Methods:

• Development of correlation consistent basis sets denoted VnZ-F12-wis (n=D,T) for d-block elements.
• Contracted basis set sizes were determined for 3d, 4d, and 5d elements.
• Evaluation using metal-organic barrier heights (MOBH35) and group-11 metal cluster (CUAGAU-2) test sets.

Main Results:

• The VnZ-F12-wis basis sets achieve accuracy close to the complete basis set limit in F12 calculations.
• Performance is comparable to using standard F12 basis sets for main-group elements and augmented basis sets for transition metals.
• The new basis sets are more compact than standard augmented sets, offering some computational time savings, particularly for metal clusters.

Conclusions:

• The developed VnZ-F12-wis basis sets are effective for F12 calculations involving d-block elements.
• These basis sets provide a balance of accuracy and efficiency for computational studies of transition metal systems.
• The findings suggest potential for improved modeling of catalytic processes and metal-containing materials.