Spectroscopy and photochemistry of copper nitrate clusters

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.