Infrared Spectroscopy of Gas Phase MnxOy(CO2)z+ Complexes.
Infrared Spectroscopy of Gas Phase MnxOy(CO2)z+ Complexes.
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DOI：
10.1021/acs.jpca.9b11258
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发表时间：
2020-01
期刊：
影响因子：
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通讯作者：
Nina Zimmermann;T. Bernhardt;J. Bakker;R. Barnett;U. Landman;S. M. Lang
中科院分区：
文献类型：
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作者：
Nina Zimmermann;T. Bernhardt;J. Bakker;R. Barnett;U. Landman;S. M. Lang
用红外多光子解离光谱研究了锰氧化物簇合物MnxOy+(x=2-5，y≥x)在630-1860 cm-1范围内与二氧化碳的相互作用。在1200-1450 cm~(-1)附近观察到两个谱带，它们是由对称伸缩振动和弯曲模泛音之间的非简谐耦合产生的CO_2的特征费米共振。低频带的光谱位置取决于团簇的大小和吸附的二氧化碳分子的数量，而高频带基本上不受影响。尽管有这些影响，对费米二分体的观察表明，二氧化碳分子只有很小的扰动。对Mn2O2(Co2)+的理论研究证实了这一发现，揭示了双锰氧化物团簇与CO2之间只有很小的轨道混合，表明主要是静电相互作用。
The interaction of manganese oxide clusters MnxOy+ (x = 2-5, y ≥ x) with CO2 is studied via infrared multiple-photon dissociation spectroscopy (IR-MPD) in the spectral region of 630-1860 cm-1. Along with vibrational modes of the manganese oxide cluster core, two bands are observed around 1200-1450 cm-1 and they are assigned to the characteristic Fermi resonance of CO2 arising from anharmonic coupling between the symmetric stretch vibration and the overtone of the bending mode. The spectral position of the lower frequency band depends on the cluster size and the number of adsorbed CO2 molecules, whereas the higher frequency band is largely unaffected. Despite these effects, the observation of the Fermi dyad indicates only a small perturbation of the CO2 molecule. This finding is confirmed by theoretical investigation of Mn2O2(CO2)+ revealing only small orbital mixing between the di-manganese oxide cluster and CO2, indicative of a mainly electrostatic interaction.