Infrared vibrational autodetachment spectroscopy of microsolvated benzonitrile radical anions
Infrared vibrational autodetachment spectroscopy of microsolvated benzonitrile radical anions
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DOI：
10.1021/jp064389
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发表时间：
2006-12-28
影响因子：
2.9
通讯作者：
Mikami, Naohiko
中科院分区：
文献类型：
--
作者：
Maeyama, Toshihiko;Yagi, Izumi;Mikami, Naohiko
微溶剂化苯甲腈自由基阴离子（C6 H5 CN-S; S = H2O和CH 3OH）的振动光谱测量通过探测在3 μ m区域的电子分离效率，代表通过OH拉伸振动的溶剂分子的自分离的共振带。与相应的中性团簇相比，两种团簇阴离子的氢键OH带都向低能侧移动了约300 cm（-1）。在用密度泛函理论优化的团簇结构中，溶剂分子与苄腈阴离子CN基团的边缘共线结合，模拟的振动能与观察到的能带位置吻合得很好.自然种群分析进行了定性的影响，在电子连接后的溶剂取向的变化。根据振动模式的不对称带的形状进行了讨论相对于自动分离过程的动力学从理论方面结合密度泛函计算。
Vibrational spectra of microsolvated benzonitrile radical anions (C6H5CN--S; S = H2O and CH3OH) were measured by probing the electron detachment efficiency in the 3 mu m region, representing resonance bands of autodetachment via OH stretching vibrations of the solvent molecules. The hydrogen-bonded OH band for both the cluster anions exhibited a large shift to the lower energy side with approximately 300 cm(-1) compared to those for the corresponding neutral clusters. The solvent molecules are bound collinearly to the edge of the CN group of the benzonitrile anion in the cluster structures optimized with the density functional theory, in which the simulated vibrational energies are in good agreement with the observed band positions. Natural population analyses were performed for a qualitative implication in changes of solvent orientation upon electron attachment. Asymmetric band shapes depending on the vibrational modes are discussed with respect to dynamics of the autodetachment process from a theoretical aspect incorporated with density functional calculations.