Spectroscopy and photochemistry of copper nitrate clusters

Literature Information

Publication Date 2021-04-06
DOI 10.1039/D1CP00629K
Impact Factor 3.676
Authors

Tobias F. Pascher, Milan Ončák, Christian van der Linde, Martin K. Beyer


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Abstract

The investigation of copper nitrate cluster anions Cu(II)n(NO3)2n+1−, n ≤ 4, in the gas phase using ultraviolet/visible/near-infrared (UV/vis/NIR) spectroscopy provides detailed insight into the electronic structure of the copper salt and its intriguing photochemistry. In the experimentally studied region up to 5.5 eV, the spectra of copper(II) nitrate exhibit a 3d–3d band in the vis/NIR and well-separated bands in the UV. The latter bands originate from Ligand-to-Metal Charge Transfer (LMCT) as well as n–π* transitions in the nitrate ligands. The clusters predominantly decompose by loss of neutral copper nitrate in the electronic ground state after internal conversion or via the photochemical loss of a neutral NO3 ligand after a LMCT. These two decomposition channels are in direct competition on the ground state potential energy surface for the smallest copper nitrate cluster, Cu(II)(NO3)3−. Here, copper nitrate evaporation is thermochemically less favorable. Population of π* orbitals in the nitrate ligands may lead to N–O bond photolysis. This is observed in the UV region with a small quantum efficiency, with photochemical loss of either nitrogen dioxide or an oxygen atom.

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

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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