Structures of platinum oxide clusters in the gas phase

Area of Science:

• Physical Chemistry
• Materials Science
• Computational Chemistry

Background:

• Understanding the behavior of small metal oxide clusters is crucial for catalysis and materials science.
• Platinum clusters are extensively studied for their catalytic properties, but their oxide forms present unique structural challenges.

Purpose of the Study:

• To elucidate the structures of small gas-phase platinum oxide cluster cations (Pt(n)O(2m)(+)).
• To investigate the binding motifs of oxygen on platinum clusters.
• To understand how oxygen binding impacts the platinum core structure.

Main Methods:

• Infrared multiple photon dissociation (IRMPD) spectroscopy was employed to probe cluster structures.
• Density functional theory (DFT) calculations were used to interpret experimental spectra and predict stable structures.

Main Results:

• Oxygen predominantly binds dissociatively to platinum clusters, favoring two-fold bridge binding sites.
• Major structural rearrangements of the platinum core occur upon oxygen incorporation.
• The presence of argon messenger atoms can significantly alter observed cluster structures for certain sizes.

Conclusions:

• The binding of oxygen dramatically modifies the intrinsic structure of platinum cluster cations.
• The study provides detailed structural insights into platinum oxide clusters, relevant for designing new catalytic materials.
• Experimental conditions, such as the use of messenger atoms, must be carefully considered when determining cluster structures.