Gas phase UV spectrum of a Cu(II)-bis(benzene) sandwich complex: experiment and theory.
J Phys Chem A
; 118(45): 10730-7, 2014 Nov 13.
Article
em En
| MEDLINE
| ID: mdl-25329443
ABSTRACT
Photofragmentation with tunable 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 â¼150 K, whereby the spectrum revealed two broad features at â¼38,200 and â¼45,700 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 Cu(2+) (d(9)) 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 (â¼10%), the theory can provide quantitative agreement with the experimental data.
Texto completo:
1
Coleções:
01-internacional
Base de dados:
MEDLINE
Assunto principal:
Benzeno
/
Cobre
/
Gases
Idioma:
En
Ano de publicação:
2014
Tipo de documento:
Article