Understanding and Quantifying London Dispersion Effects in Organometallic Complexes

Area of Science:

• Computational Chemistry
• Quantum Mechanics
• Materials Science

Background:

• Standard density functional approximations struggle with long-range electron correlation (London dispersion).
• Dispersion effects are crucial for accurate chemical property prediction, especially in organometallic systems.

Purpose of the Study:

• To evaluate the accuracy of DFT-D4 for calculating structural and thermodynamic properties of organometallic complexes.
• To highlight the importance of dispersion corrections in organometallic chemistry and catalysis.

Main Methods:

• Utilized Kohn-Sham density functional theory (DFT) with the D4 dispersion correction.
• Included atomic partial charge information in dispersion calculations.
• Applied the method to various organometallic complexes and main group compounds.

Main Results:

• DFT-D4 accurately predicts gas-phase thermochemistry and structures for organometallic complexes.
• Dispersion interactions significantly influence the accuracy of computed reaction energies.
• Atomic charge information in DFT-D4 improves dispersion energy calculations, particularly for metallic systems.

Conclusions:

• The DFT-D4 method offers an excellent accuracy-to-cost ratio for studying organometallic systems.
• Accurate structural and thermodynamic data are essential for designing dispersion-controlled reactions and catalysts.
• DFT-D4's efficiency allows its application to a wide range of chemical methods.