A Matrix Isolation and Computational Study of Molecular Palladium Fluorides: Does PdF6 Exist?

Area of Science:

• Inorganic Chemistry
• Spectroscopy
• Computational Chemistry

Background:

• Palladium fluorides are of interest due to their unique chemical properties.
• Previous studies have explored various palladium fluoride species, but definitive characterization remains challenging.

Purpose of the Study:

• To synthesize and characterize palladium fluoride molecules formed in low-temperature matrices.
• To investigate the existence and properties of palladium hexafluoride (PdF6).

Main Methods:

• Palladium atoms were generated via thermal evaporation and laser ablation.
• Reactions were conducted in fluorine/argon, fluorine/neon, and neat fluorine matrices.
• Characterization involved electronic absorption and infrared spectroscopy.
• Relativistic density functional theory and coupled cluster calculations were employed.

Main Results:

• Vibrational modes were assigned to molecular PdF, PdF2, and PdF4 in argon matrices.
• A band at 624 cm(-1) was tentatively assigned to PdF3 or PdF6, with PdF3 favored experimentally.

Conclusions:

• The study successfully identified PdF, PdF2, and PdF4 molecules.
• Despite computational support for PdF6, experimental evidence was not convincing, suggesting its absence under these conditions.