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Size-Dependent Onset of Nitric Acid Dissociation in Cs+·(HNO3)(H2O)n=0–11 Clusters at 20 K
The Journal of Physical Chemistry Letters ( IF 4.8 ) Pub Date : 2021-03-29 , DOI: 10.1021/acs.jpclett.1c00235 Sayoni Mitra 1 , Nan Yang 1 , Laura M. McCaslin 2 , R. Benny Gerber 3, 4 , Mark A. Johnson 1
The Journal of Physical Chemistry Letters ( IF 4.8 ) Pub Date : 2021-03-29 , DOI: 10.1021/acs.jpclett.1c00235 Sayoni Mitra 1 , Nan Yang 1 , Laura M. McCaslin 2 , R. Benny Gerber 3, 4 , Mark A. Johnson 1
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We report the water-mediated charge separation of nitric acid upon incorporation into size-selected Cs+·(HNO3)(H2O)n=0–11 clusters at 20 K. Dramatic spectral changes are observed in the n = 7–9 range that are traced to the formation of many isomeric structures associated with intermediate transfer of the acidic proton to the water network. This transfer is complete by n = 10, which exhibits much simpler vibrational band patterns consistent with those expected for a tricoordinated hydronium ion (the Eigen motif) along with the NO stretching bands predicted for a hydrated NO3– anion that is directly complexed to the Cs+ cation. Theoretical analysis of the n = 10 spectrum indicates that the dissociated ions adopt a solvent-separated ion-pair configuration such that the Cs+ and H3O+ cations flank the NO3– anion in a microhydrated salt bridge. This charge separation motif is evidently assisted by the electrostatic stabilization of the product NO3–/H3O+ ion pair by the proximal metal ion.
中文翻译：
在20 K下Cs + ·（HNO 3）（H 2 O）n = 0–11簇中硝酸离解的尺寸依赖性开始
我们报道了在20 K时，水介导的硝酸中硝酸的电荷分离，其被引入到大小选择的Cs + ·（HNO 3）（H 2 O）n = 0–11簇中。在n = 7– 9的范围可追溯到与酸性质子向水网络的中间转移相关的许多异构结构的形成。这种转移是通过完全Ñ = 10，其显示出与预测水合NO的NO伸缩带沿简单得多振动带图案与预期用于tricoordinated水合氢离子（本征基序）一致的3 -的阴离子，其直接络合到Cs +阳离子。所述的理论分析Ñ = 10光谱表明，离解的离子采用溶剂分离的离子对的构型，使得在Cs +和H 3 ö +阳离子侧翼的NO 3 -的阴离子的microhydrated盐桥。此电荷分离基序显然由产品NO的静电稳定辅助3 - / H 3 ö +由近侧金属离子的离子对。
更新日期：2021-04-08
中文翻译：
在20 K下Cs + ·（HNO 3）（H 2 O）n = 0–11簇中硝酸离解的尺寸依赖性开始
我们报道了在20 K时，水介导的硝酸中硝酸的电荷分离，其被引入到大小选择的Cs + ·（HNO 3）（H 2 O）n = 0–11簇中。在n = 7– 9的范围可追溯到与酸性质子向水网络的中间转移相关的许多异构结构的形成。这种转移是通过完全Ñ = 10，其显示出与预测水合NO的NO伸缩带沿简单得多振动带图案与预期用于tricoordinated水合氢离子（本征基序）一致的3 -的阴离子，其直接络合到Cs +阳离子。所述的理论分析Ñ = 10光谱表明，离解的离子采用溶剂分离的离子对的构型，使得在Cs +和H 3 ö +阳离子侧翼的NO 3 -的阴离子的microhydrated盐桥。此电荷分离基序显然由产品NO的静电稳定辅助3 - / H 3 ö +由近侧金属离子的离子对。
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