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Gas phase UV spectrum of a Cu(II)–Bis(benzene) sandwich complex: experiment and theory
journal contribution
posted on 2023-06-08, 20:42 authored by Lifu Ma, Joseph Koka, Anthony J Stace, Hazel CoxHazel CoxPhotofragmentation with tuneable UV radiation has been used to generate a spectrum for the copper-bis(benzene) complex, [Cu(C6H6)2]2+ in the gas phase. The ions were held in an ion trap where their temperature was reduced to ~150 K, whereby the spectrum revealed two broad features at ~38200 cm-1 and ~45700 cm-1. Detailed calculations using density functional theory (DFT) show the complex can occupy three minimum energy structures with C2v and C2 (staggered and eclipsed) symmetries. Adiabatic time-dependent DFT (TDDFT) has been used to identify electronic transitions in [Cu(benzene)2]2+ and the calculations show these to fall into two groups that are in excellent agreement with the experimental data. However, the open-shell electronic configuration of Cu2+ (d9) may give rise to excited states with double-excitation character and the single-excitation adiabatic TDDFT treatment leads to extensive spin contamination. By quantifying the extent of spin contamination and allowing for the inclusion of a small percentage (~10 %), the theory can provide quantitative agreement with the experimental data.
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Publication status
- Published
Journal
Journal of Physical Chemistry AISSN
1089-5639Publisher
American Chemical SocietyExternal DOI
Issue
45Volume
118Page range
10730-10737Department affiliated with
- Chemistry Publications
Full text available
- No
Peer reviewed?
- Yes
Legacy Posted Date
2015-05-07Usage metrics
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