Neumann Stefanie, Eisfeld Wolfgang, Sobolewski Andrzej L, Domcke Wolfgang
Department of Chemistry, Technical University of Munich, Garching, Germany.
J Phys Chem A. 2006 May 4;110(17):5613-9. doi: 10.1021/jp0574549.
The microsolvation of the CH(3)OH(2) hypervalent radical in methanol clusters has been investigated by density functional theory. It is shown that the CH(3)OH(2) radical spontaneously decomposes within methanol clusters into protonated methanol and a localized solvated electron cloud. The geometric and electronic structures of these clusters as well as their vibrational frequencies have been characterized. Resonance Raman intensities, associated with the s --> p transition of the unpaired electron, have been estimated for CH(3)OH(2)M(n) (M = CH(3)OH, n = 1-3) clusters. It is shown that with increasing cluster size the simulated spectra converge toward the resonance Raman spectrum of the solvated electron in methanol measured recently by Tauber and Mathies (J. Am. Chem. Soc. 2004, 126, 3414). The results suggest that CH(3)OH(2)M(n) clusters are useful finite-size model systems for the computational investigation of the spectroscopic properties of the solvated electron in liquid methanol.
通过密度泛函理论研究了甲醇团簇中CH(3)OH(2)超价自由基的微溶剂化作用。结果表明，CH(3)OH(2)自由基在甲醇团簇中自发分解为质子化甲醇和局部溶剂化电子云。对这些团簇的几何和电子结构以及它们的振动频率进行了表征。估算了与未成对电子的s→p跃迁相关的CH(3)OH(2)M(n)（M = CH(3)OH，n = 1 - 3）团簇的共振拉曼强度。结果表明，随着团簇尺寸的增加，模拟光谱趋向于Tauber和Mathies最近测量的甲醇中溶剂化电子的共振拉曼光谱（《美国化学会志》2004年，126卷，3414页）。结果表明，CH(3)OH(2)M(n)团簇是用于计算研究液态甲醇中溶剂化电子光谱性质的有用有限尺寸模型系统。
