Does spin-orbit coupling effect favor planar structures for small platinum clusters?

Area of Science:

• Physical Chemistry
• Computational Chemistry
• Materials Science

Background:

• Platinum clusters exhibit unique properties influenced by size and electronic structure.
• Understanding cluster isomers and their stability is crucial for designing new materials.
• Spin-orbit coupling can significantly impact electronic and geometric properties of heavy element systems.

Purpose of the Study:

• To investigate the geometric and binding energy of platinum clusters (Pt(n), n=4-6).
• To analyze the impact of spin-orbit coupling on cluster properties.
• To determine the lowest energy structures and relative stabilities of platinum cluster isomers.

Main Methods:

• Relativistic effective core potential calculations.
• Density functional theory (DFT) framework.
• Inclusion and exclusion of spin-orbit coupling term.
• Analysis of spin multiplicities from singlet to nonet.

Main Results:

• Three-dimensional (3-D) configurations are generally the lowest energy structures for Pt(n) clusters (n=4-6).
• Spin-orbit coupling (SOC) impacts the relative stability of different isomers.
• SOC can enhance the stability of some planar or quasi-planar geometries compared to certain 3-D isomers.
• SOC influences vibrational frequencies, magnetic moments, and molecular orbital gaps.

Conclusions:

• Spin-orbit coupling is a significant factor in determining the properties of platinum clusters.
• The interplay between cluster geometry, spin multiplicity, and SOC is complex.
• DFT calculations with SOC provide a more accurate description of platinum cluster behavior.