Exploring the nature of the excitation energies in [Re6(μ3-Q8)X6]4− clusters: a relativistic approach
Literature Information
Walter A. Rabanal-León, Dayán Páez-Hernández, Ramiro Arratia-Pérez
This contribution is a relativistic theoretical study to characterize systematically the main electronic transitions in a series of hexarhenium chalcogenide [Re6(μ3-Q8)X6]4− clusters with the aim of understanding: (i) the terminal ligand substitution effect, (ii) the substitution effect of the chalcogenide ion on the [Re6(μ3-Q8)]2+core, and finally (iii) the significance of the spin–orbit coupling (SOC) effect on the optical selection rules. In all the cases, we found characteristic bands at around 300–550 nm, where the band positions are directly determined by the terminal ligand. However, SCN−/NCS− presents a different nature of the orbitals involved in the electronic transitions, in comparison with the other studied terminal ligands, located in the near-infrared (NIR) region. All the bands are red-shifted as a consequence of the ligand contribution in the composition of the orbitals involved in the electronic excitations.
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.









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