Ground‐State Structure of the Proton‐Bound Formate Dimer by Cold‐Ion Infrared Action Spectroscopy,Angewandte Chemie International Edition

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Ground‐State Structure of the Proton‐Bound Formate Dimer by Cold‐Ion Infrared Action Spectroscopy
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2018-07-12 , DOI: 10.1002/anie.201805436
Daniel A. Thomas ₁ , Mateusz Marianski ₁ , Eike Mucha ₁ , Gerard Meijer ₁ , Mark A. Johnson ₂ , Gert von Helden ₁

Affiliation

The proton‐bound dicarboxylate motif, RCOO⁻⋅H⁺⋅⁻OOCR, is a prevalent chemical configuration found in many condensed‐phase systems. The proton‐bound formate dimer HCOO⁻⋅H⁺⋅⁻OOCH was studied utilizing cold‐ion IR action spectroscopy in the range 400–1800 cm⁻¹. The spectrum obtained at ca. 0.4 K of ions captured in He nanodroplets was compared to that measured at ca. 10 K by photodissociation of Ar‐ion complexes. Similar band patterns are obtained by the two techniques that are consistent with calculations for a C₂ symmetry structure with a proton shared equally between the two formate moieties. Isotopic substitution experiments point to the nominal parallel stretch of the bridging proton appearing as a sharp, dominant feature near 600 cm⁻¹. Multidimensional anharmonic calculations reveal that the bridging proton motion is strongly coupled to the flanking −COO⁻ framework, an effect that is in line with the expected change in −C=O bond rehybridization upon protonation.

中文翻译：

质子-结合甲二聚体的基态结构的冷离子红外光谱研究

质子结合的二羧酸酯基序RCOO ^- ⋅H ⁺ ⋅ ^- OOCR是许多冷凝相系统中常见的化学构型。质子结合的甲酸酯二聚体HCOO ^- ⋅H ⁺ ⋅ ^- OOCH是利用冷离子红外光谱在400–1800 cm ^-1范围内研究的。大约在将在He纳米液滴中捕获的0.4 K离子与在约200 nm下测得的离子进行比较。Ar离子络合物的光解离可得10K。通过两种技术获得与C _2的计算一致的相似的带模式两个甲酸部分之间均等地共享具有质子的对称结构。同位素替代实验指出，桥接质子的标称平行拉伸在600 cm ^-1附近表现为明显的显性特征。多维非谐计算表明桥接质子运动强烈耦合到侧翼-COO ^-框架，即在与-C = O键重新杂交在质子化时的预期变化线的效果。

更新日期：2018-07-12

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