Citation: Qiuying Du, Baoqi Yin, Si Zhou, Zhixun Luo, Jijun Zhao. The reactivity of O₂ with copper cluster anions Cu_n⁻ (n = 7−20): Leveling effect of spin accommodation[J]. Chinese Chemical Letters, ;2022, 33(2): 995-1000. doi: 10.1016/j.cclet.2021.08.127 shu

The reactivity of O₂ with copper cluster anions Cu_n⁻ (n = 7−20): Leveling effect of spin accommodation

Qiuying Du ^{a, 1} ,
Baoqi Yin ^{b, 1} ,
Si Zhou ^{a, *,} ,
Zhixun Luo ^{b, *,} ,
Jijun Zhao ^a

a.
Key laboratory of Material Modification by Laser, Ion and Electron Beams (Dalian University of Technology), Ministry of Education, Dalian 116024, China
b.
Beijing National Laboratory for Molecular Sciences (BNLMS), State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China

sizhou@dlut.edu.cn

zxluo@iccas.ac.cn

Received Date: 7 July 2021
Revised Date: 27 July 2021
Accepted Date: 31 August 2021
Available Online: 6 September 2021

Figures(6)

The activation of molecular oxygen is an important step in metal-catalyzed oxidation reactions and a hot subject for the research of gas-phase metal clusters. It is known that the Ag and Au clusters readily react with O₂ when they have open shell electronic structures. Distinct from this, here we observed Cu_n⁻ (n = 7−20) clusters of both open and closed shells possess high reactivity with O₂ with few exceptions. In a combination with ab initio calculations, we demonstrate that the activation of O₂ on the even- and odd-sized Cu_n⁻ clusters follows the single and double electron transfer models, respectively. Such phenomenon of metal clusters with different basicity to activate oxygen is enabled by the leveling effect of spin accommodation. The activity of Cu_n⁻ clusters is correlated to the HOMO level, and for the close-shell clusters is also governed by the vertical spin excitation energy (VSE). In encountering the attack of dioxygen, the activity of the copper cluster anions not only depends on their basicity to donate electrons, but also closely associated with the cluster sizes. Small copper clusters Cu_n⁻ (n = 7−13) can dissociate O₂ spontaneously, while large clusters require extra energies and display close relationship between the reaction rates and electronic vertical detachment energies (VDE). Our work illuminates a novel reaction mechanism between Cu_n⁻ clusters and O₂, which sheds light in manipulating the activity and stability of coinage clusters by controlling the spin and charge states.
- Copper cluster,
- Mass spectrometry,
- Ab initio,
- O₂ adsorption,
- O₂ dissociation,
- Leveling effect,
- Spin accommodation
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The reactivity of O2 with copper cluster anions Cun− (n = 7−20): Leveling effect of spin accommodation

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The reactivity of O₂ with copper cluster anions Cu_n⁻ (n = 7−20): Leveling effect of spin accommodation