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首页> 外文期刊>The Journal of Chemical Physics >The vibrational predissociation spectra of the H_5O_2~+centre dotRG_n(RG=Ar,Ne) clusters:Correlation of the solvent perturbations in the free OH and shared proton transitions of the Zundel ion
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The vibrational predissociation spectra of the H_5O_2~+centre dotRG_n(RG=Ar,Ne) clusters:Correlation of the solvent perturbations in the free OH and shared proton transitions of the Zundel ion

机译：H_5O_2〜+中心点RG_n（RG = Ar，Ne）团簇的振动预解离谱：自由OH中的溶剂扰动与Zundel离子的质子跃迁的相关性

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摘要

Predissociation spectra of the H_5O_2~+centre dotRG_n(RG=Ar,Ne) cluster ions are reported in energy regions corresponding to both the OH stretching (3350-3850 cm~(-1)) and shared proton (850-1950 cm~(-1)) vibrations.The two free OH stretching bands displayed by the Ne complex are quite close to the band origins identified earlier in bare H_5O_2~+ [L.I.Yeh,M.Okumura,J.D.Myers,J.M.Price,and Y.T.Lee,J.Chem.Phys.91,7319 (1989)],indicating that the symmetrical H_5O_2~+ "Zundel" ion remains largely intact in H_5O_2~+centre dot Ne.The low-energy spectrum of the Ne complex is simpler than that observed previously for H_5O_2~+centre dotAr,and is dominated by two sharp transitions at 928 and 1047 cm~(-1),with a weaker feature at 1763 cm~(-1).The H_5O_2~+centre dot Ar_n,n=1-5 spectra generally exhibit complex band structures reflecting solvent-induced symmetry breaking of the Zundel core ion.The extent of solvent perturbation is evaluated with electronic structure calculations,which predict that the rare gas atoms should attach to the spectator OH groups of H_5_2~+ rather than to the shared proton.In the asymmetric complexes,the shared proton resides closer to the more heavily solvated water molecule,leading to redshifts in the rare gas atom-solvated OH stretches and to blueshifts in the shared proton vibrations.The experimental spectra are compared with recent full-dimensional vibrational calculations (diffusion Monte Carlo and multimode/vibrational configuration interaction) on H_5O_2~+.These results are consistent with assignment of the strong low-energy bands in the H_5O_2~+centre dotNe spectrum to the vibration of the shared proton mostly along the O-O axis,with the 1763 cm~(-1) band traced primarily to the out-of-phase,intramolecular bending vibrations of the two water molecules.
机译：在与OH拉伸（3350-3850 cm〜（-1））和共享质子（850-1950 cm〜（）对应的能量区域中报告了H_5O_2〜+中心点RG_n（RG = Ar，Ne）簇离子的预离解谱-1））振动。由Ne络合物显示的两个自由OH拉伸带与早期在裸露的H_5O_2〜+ [LIYeh，M.Okumura，JDMyers，JMPrice和YTLee，J [Chem.Phys.91,7319（1989）]，表明对称的H_5O_2〜+“ Zundel”离子在H_5O_2〜+中心Ne中基本上保持完整。Ne络合物的低能谱比以前观察到的更简单H_5O_2〜+中心点Ar，主要由928和1047 cm〜（-1）处的两个尖锐跃迁所控制，在1763 cm〜（-1）处具有较弱的特征。H_5O_2〜+中心点Ar_n，n = 1- 5个光谱通常表现出复杂的能带结构，反映了溶剂诱导的Zundel核心离子对称性断裂。通过电子结构计算来评估溶剂扰动的程度，从而预测稀有气体原子应附着在H_5_2〜+的观众OH基团上，而不是共享的质子上。在不对称的配合物中，共享的质子更靠近溶剂化程度更高的水分子，导致稀有气体原子溶解后发生红移OH在质子共享振动中伸展并发生蓝移。将实验光谱与H_5O_2〜+上的全维振动计算（蒙特卡罗扩散和多模/振动构型相互作用）进行了比较，这些结果与强低辐射的分配相一致。 H_5O_2〜+中心点Ne谱中的能带对共享质子的振动主要沿OO轴，其中1763 cm〜（-1）的能带主要是两种水的异相分子内弯曲振动分子。

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