Insights into the geometries, electronic and magnetic properties of neutral and charged palladium clusters

We performed an unbiased structure search for low-lying energetic minima of neutral and charged palladium Pd(n)(Q) (n = 2–20, Q = 0, + 1 and –1) clusters using CALYPSO method in combination with density functional theory (DFT) calculations. The main candidates for the lowest energy neutral, cationic and anionic clusters are identified, and several new candidate structures for the cationic and anionic ground states are obtained. It is found that the ground state structures of small palladium clusters are more sensitive to the charge states. For the medium size Pd(n)(0/+/–) (n = 16–20) clusters, a fcc-like growth behavior is found. The structural transition from bilayer-like structures to cage-like structures is likely to occur at n = 14 for the neutral and cationic clusters. In contrast, for the anionic counterparts, the structural transition occurs at Pd(13)(–). The photoelectron spectra (PES) of palladium clusters are simulated based on the time-dependent density functional theory (TD-DFT) method and compared with the experimental data. The good agreement between the experimental PES and simulated spectra provides us unequivocal structural information to fully solve the global minimum structures, allowing for new molecular insights into the chemical interactions in the Pd cages

Complete Active Space Wavefunction-Based Analysis of Magnetization and Electronic Structure

International audienceA theoretical framework for the generation of natural orbitals, naturalspin orbitals, as well as orbital- and spin-magnetizations from multi-configurationalab-initio wavefunction calculations including spin-orbit coupling is presented. It isshown how these computational orbital and magnetization tools can be used to inter-pret and rationalize the magnetic properties of selected complexes containing tran-sition metals, lanthanides, and actinides