The shortest Th–Th distance from a new type of quadruple bond
文献信息
Han-Shi Hu, Nikolas Kaltsoyannis
Compounds featuring unsupported metal–metal bonds between actinide elements remain highly sought after yet confined experimentally to inert gas matrix studies. Notwithstanding this paucity, actinide–actinide bonding has been the subject of extensive computational research. In this contribution, high level quantum chemical calculations at both the scalar and spin–orbit levels are used to probe the Th–Th bonding in a range of zero valent systems of general formula LThThL. Several of these compounds have very short Th–Th bonds arising from a new type of Th–Th quadruple bond with a previously unreported electronic configuration featuring two unpaired electrons in 6d-based δ bonding orbitals. H3AsThThAsH3 is found to have the shortest Th–Th bond yet reported (2.590 Å). The Th2 unit is a highly sensitive probe of ligand electron donor/acceptor ability; we can tune the Th–Th bond from quadruple to triple, double and single by judicious choice of the L group, up to 2.888 Å for singly-bonded ONThThNO.
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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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