Oomens Jos, Moore David T, Von Helden Gert, Meijer Gerard, Dunbar Robert C
FOM Institute for Plasma Physics "Rijnhuizen", Postbus 1207, 3430 BE Nieuwegein, The Netherlands.
J Am Chem Soc. 2004 Jan 28;126(3):724-5. doi: 10.1021/ja038867v.
Infrared spectroscopy of gas-phase Cr+ complexes of aniline was studied using the FELIX free electron laser interfaced to a Fourier transform ion cyclotron resonance spectrometer. For both the monomer complex Cr+(aniline) and the dimer complex Cr+(aniline)2 the spectra showed features indicating binding of the metal ion to the aromatic pi cloud, as opposed to the nitrogen atom. Agreement with DFT-calculated infrared absorption spectra for the ring-bound complexes was good using the MPW1PW91 functional, but the B3LYP functional predicted the wrong binding site. The spectroscopic results resolve the ambiguity in computational prediction of the preferred binding site and support the use of the MPW1PW91 functional for these systems.
利用与傅里叶变换离子回旋共振光谱仪相连的FELIX自由电子激光，研究了气相中铬离子与苯胺形成的配合物的红外光谱。对于单体配合物Cr⁺(苯胺)和二聚体配合物Cr⁺(苯胺)₂，光谱显示出一些特征，表明金属离子与芳香π云结合，而非与氮原子结合。使用MPW1PW91泛函时，与环结合配合物的密度泛函理论(DFT)计算的红外吸收光谱吻合良好，但B3LYP泛函预测的结合位点错误。光谱结果解决了计算预测优先结合位点时的模糊性，并支持在这些体系中使用MPW1PW91泛函。
