Theoretical Vibrational Spectroscopy of Aqueous Solutions

振动光谱学是长期以来用于研究水体系结构和动力学的一种强有力的方法。几十年来，高频分子内模式被用作中红外频率范围内的特定报告模式，而不久前，人们发现通过探测远红外区域的低频分子间运动可以获得丰富的互补信息。后一种模式最直接地耦合到氢键网络动力学中，因此是水环境中复杂网络动力学的报告者。利用、扩展和推广在第一个资助期开发和应用的技术，定量计算和完全分配一般均质大块水系统的远红外光谱，现在建议在第二步中处理重要的非均质界面系统以及气相中的有限簇。

Vibrational spectroscopy is a powerful approach employed since long to investigate the structure and dynamics of aqueous systems. Since decades, high-frequency intra-molecular modes have been used as specific reporter modes in the mid-infrared frequency range, whereas not long ago it has been found that a wealth of complementary information can be gained by probing low-frequency inter-molecular motion in the far-infrared regime. The latter modes couple most directly into the hydrogen-bond network dynamics and are thus reporters for the intricate network dynamics in aqueous environments. Using, extending, and generalizing the techniques that have been developed and applied in the first funding period to quantitatively compute and fully assign far-infrared spectra of generic homogeneous bulk water systems, it is now proposed to tackle in a second step important such inhomogeneous interfacial systems as well as finite clusters in the gas phase.