Gas phase UV spectrum of a Cu(II)–Bis(benzene) sandwich complex: experiment and theory

Ma, Lifu, Koka, Joseph, Stace, Anthony J and Cox, Hazel (2014) Gas phase UV spectrum of a Cu(II)–Bis(benzene) sandwich complex: experiment and theory. Journal of Physical Chemistry A, 118 (45). pp. 10730-10737. ISSN 1089-5639

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Abstract

Photofragmentation 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.

Item Type: Article
Schools and Departments: School of Life Sciences > Chemistry
Subjects: Q Science > QD Chemistry > QD0450 Physical and theoretical chemistry
Depositing User: Hazel Cox
Date Deposited: 07 May 2015 08:46
Last Modified: 07 May 2015 08:46
URI: http://sro.sussex.ac.uk/id/eprint/53890
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