Reactions of laser-ablated Cu with NO:: Infrared spectra and density functional calculations of CuNO+, CuNO, Cu(NO)2, and Cu(NO)2- in solid neon and argon

Laser-ablated copper atoms react with NO molecules in excess neon and argon during condensation to form the CuNO and Cu(NO)(2) complexes as major products and Cu(NO)(2)(NO)* as a minor product. In addition, the CuNO+ cation and Cu(NO)(2)(-) anion are also formed. The product absorptions are identified from isotopic shifts and splitting patterns in the matrix infrared spectra and are supported by DFT calculations of isotopic frequencies. Sequential annealing increases CuNO and Cu(NO)(2), and then CuNO gives way to Cu(NO)(2) and Cu(NO)(2)(NO)*, a dinitrosyl with a third inequivalent NO subgroup. The isolated mononitrosyl and dinitrosyl species provide a scale to estimate local charge on CuNO and Cu(NO)(2) sites in Cu-exchanged zeolite catalyst systems.