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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Identification of Two Distinct Electron Binding Motifs in the Anionic Water Clusters:A Vibrational Spectroscopic Study of the (H_2O)_6~- Isomers
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Identification of Two Distinct Electron Binding Motifs in the Anionic Water Clusters:A Vibrational Spectroscopic Study of the (H_2O)_6~- Isomers

机译：阴离子水团簇中两个不同的电子结合基元的鉴定：（H_2O）_6〜-异构体的振动光谱研究

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Photoelectron spectroscopy of the water cluster anions,(H_2O)_n~-,has revealed that several isomeric forms are present for most sizes,and here,we use vibrational spectroscopy to address the structure of the (H_2O)_6~-isomer that more weakly binds the extra electron.To overcome the severe line broadening that occurs in the OH stretching region of this isomer caused by fast electron autodetachment,we concentrate on the low-energy bending modes of the perdeutero isotopomer.Sharp spectroscopic signatures are recovered for two isomers using argon predissociation spectroscopy,and the resulting bands are heavily overlapped.To extract their independent contributions to the observed spectra,we exploit the substantial dependence of their relative populations on the number of attached argon atoms in the (D_2O)_6~- centre dot Ar_m clusters,determined by photoelectron spectroscopy.The vibrational spectra of each isomer can then be isolated by spectral subtraction,which is implemented with a covariance mapping approach.The resulting band patterns establish that the more weakly binding isomer does not display the characteristic electron-binding motif common to the more strongly bound isomer class.Whereas the strongly binding isomer features a single water molecule pointing toward the excess electron cloud with both of its hydrogen atoms,the spectrum of the more weakly binding isomer suggests a structure where the electron is bound by a number of dangling OH groups corresponding to water molecules in acceptor-donor binding sites.
机译：水簇阴离子（H_2O）_n〜-的光电子能谱显示大多数尺寸都存在几种异构形式，在这里，我们使用振动光谱法来研究（H_2O）_6〜-异构体的结构为了克服由于快速电子自分离导致的异构体在OH延伸区出现的严重谱线展宽问题，我们着重研究了Perdeutero同位素的低能弯曲模式。使用2个异构体回收了锋利的光谱特征为了分离出它们对观测光谱的独立贡献，我们利用了它们的相对种群对（D_2O）_6〜-中心点Ar_m团簇中附着的氩原子数的显着依赖性，以提取它们对观测光谱的独立贡献。 ，然后通过光谱减法分离出每个异构体的振动光谱，这可以通过协变量实现因此，能带图谱表明结合较弱的异构体未显示出与结合更强的异构体类别相同的特征性电子结合基序，而结合强的异构体则具有一个指向多余电子云的水分子结合较弱的异构体的光谱表明，其结构是电子被多个悬垂的OH基团束缚的结构，该悬空的OH基团对应于受体与供体的结合位点中的水分子。

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