Nitrogen adsorption on Nb2C6H4+ cations: the important role of benzyne (ortho-C6H4)
Literature Information
Feng-Xiang Zhang, Yi-Heng Zhang, Ming Wang, Jia-Bi Ma
N2 adsorption is a prerequisite for activation and transformation. Time-of-flight mass spectrometry experiments show that the Nb2C6H4+ cation, resulting from the gas-phase reaction of Nb2+ with C6H6, is more favorable for N2 adsorption than Nb+ and Nb2+ cations. Density functional theory calculations reveal the effect of the ortho-C6H4 ligand on N2 adsorption. In Nb2C6H4+, interactions between the Nb-4d and C-2p orbitals enable the Nb2+ cation to form coordination bonds with the ortho-C6H4 ligand. Although the ortho-C6H4 ligand in Nb2C6H4+ is not directly involved in the reaction, its presence increases the polarity of the cluster and brings the highest occupied molecular orbital (HOMO) closer to the lowest occupied molecular orbital (LUMO) of N2, thereby increasing the N2 adsorption energy, which effectively facilitates N2 adsorption and activation. This study provides fundamental insights into the mechanisms of N2 adsorption in “transition metal–organic ligand” systems.
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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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