Two isomers of CuO2: The Cu(O2) complex and the copper dioxide

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Abstract
Photoelectron spectroscopy of CuO−2 has been studied at three detachment wavelengths: 532 nm, 355 nm, and 266 nm. Vibrationally resolved spectra for two distinct isomers are observed: the Cu(O2) complex and the copper dioxide molecule. The Cu(O)2 complex has an electron affinity (EA) of 1.503 (10) eV with a ground state vibrational frequency of 530 (50) cm−1. Its first electronic excited state is 7400 (300) cm−1 above the ground state. The Cu(O2)− anion is also observed to undergo photodissociation to Cu−+O2 at both 532 nm and 355 nm detachment wavelengths. The copper dioxide molecule is found to have a high EA of 3.46 (4) eV. Three low‐lying excited states are observed within 1 eV above the ground state. The first two excited states of the copper dioxide molecule both possess a totally symmetric vibrational frequency of 640 (60) cm−1.