论文标题
质子化水二聚体的状态分辨红外光谱：重新审视特征性质子转移双线峰
State-resolved infrared spectrum of the protonated water dimer: Revisiting the characteristic proton transfer doublet peak
论文作者
论文摘要
质子化水簇的红外光谱编码有关水合质子动力学和结构的精确信息。但是，这些难以捉摸的物种的强烈无谐耦合和量子效应一直困扰着今天。在这里，我们报告了明确的证据，表明质子转移与质子化水二聚体（Zundel离子）中的水的相互作用，从而引起了特征性的Doublet峰，既比以前认为的对精力的变化更为复杂，更敏感。尤其是，迄今忽略了实验光谱中低强度的卫星峰，现在已经揭幕并机械地分配了。我们的发现依赖于使用两个高度准确的势能表面获得的IR光谱的比较以及高度准确的状态分辨量子模拟。我们证明，这些高临界模拟对于提供通量分子的复杂IR信号的确定分配很重要。
The infrared (IR) spectra of protonated water clusters encode precise information on the dynamics and structure of the hydrated proton. However, the strong anharmonic coupling and quantum effects of these elusive species remain puzzling up to the present day. Here, we report unequivocal evidence that the interplay between the proton transfer and the water wagging motions in the protonated water dimer (Zundel ion) giving rise to the characteristic doublet peak is both more complex and more sensitive to subtle energetic changes than previously thought. In particular, hitherto overlooked low-intensity satellite peaks in the experimental spectrum are now unveiled and mechanistically assigned. Our findings rely on the comparison of IR spectra obtained using two highly accurate potential energy surfaces in conjunction with highly accurate state-resolved quantum simulations. We demonstrate that these high-accuracy simulations are important for providing definite assignments of the complex IR signals of fluxional molecules.
