Department of Chemistry, Temple University, Philadelphia, Pennsylvania 19122, USA.
J Am Chem Soc. 2010 Mar 24;132(11):3756-61. doi: 10.1021/ja907745r.
Time-resolved sum frequency generation (tr-SFG) reveals that the vibrational energy relaxation rate of O-H stretching of dilute HDO in D(2)O at the silica interface is markedly different from that of bulk water. As compared to the bulk liquid, the vibrational lifetime (T(1)) of HDO is shorter at the charged surface than in the bulk, but longer at the neutral surface. The vibrational decoupling of the O-H of the HDO species leads to the observation of a frequency-dependent T(1) of the O-H stretch, which is shorter at the red than the blue side of the hydrogen-bonded OH spectral region. This correlates with the red-shift of the SFG spectra with increasing surface charge and is consistent with a theoretical model that relates the vibrational lifetime to the strength of the hydrogen-bond network.
时间分辨和频发生（tr-SFG）表明，在二氧化硅界面处稀 HDO 中 O-H 伸缩振动的振动能量弛豫速率与体相水明显不同。与体相液体相比，带电荷表面处 HDO 的振动寿命（T(1)）比在体相时短，但在中性表面处则更长。HDO 物种的 O-H 振动去耦导致观察到 O-H 伸缩的频率相关 T(1)，在氢键 OH 光谱区域的红色一侧比蓝色一侧更短。这与随着表面电荷增加 SFG 光谱的红移相关，并且与将振动寿命与氢键网络强度相关联的理论模型一致。
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