Department of Chemistry, University of Southern California, Los Angeles, California 90089-0482, USA.
J Phys Chem A. 2011 Jun 30;115(25):6903-9. doi: 10.1021/jp112024s. Epub 2011 Mar 9.
The state-to-state vibrational predissociation (VP) dynamics of the hydrogen-bonded HCl-H(2)O dimer was studied following excitation of the dimer's HCl stretch by detecting the H(2)O fragment. Velocity map imaging (VMI) and resonance-enhanced multiphoton ionization (REMPI) were used to determine pair-correlated product energy distributions. Following vibrational excitation of the HCl stretch of the dimer, H(2)O fragments were detected by 2 + 1 REMPI via the C (1)B(1) (000) ← X (1)A(1) (000) transition. REMPI spectra clearly show H(2)O from dissociation produced in the ground vibrational state. The fragments' center-of-mass (c.m.) translational energy distributions were determined from images of selected rotational states of H(2)O and were converted to rotational state distributions of the HCl cofragment. The distributions were consistent with the previously measured dissociation energy of D(0) = 1334 ± 10 cm(-1) and show a clear preference for rotational levels in the HCl fragment that minimize translational energy release. The usefulness of 2 + 1 REMPI detection of water fragments is discussed.
氢键 HCl-H(2)O 二聚体的态态振动预解离 (VP) 动力学研究了通过检测 H(2)O 碎片来激发二聚体的 HCl 伸缩振动后的情况。速度图成像 (VMI) 和共振增强多光子电离 (REMPI) 用于确定对相关产物能量分布。在二聚体的 HCl 伸缩振动被激发后,通过 2 + 1 REMPI 通过 C (1)B(1) (000) ← X (1)A(1) (000) 跃迁检测到 H(2)O 碎片。REMPI 光谱清楚地显示了来自基态振动状态解离产生的 H(2)O。通过对 H(2)O 选定转动态的图像进行分析,确定了碎片的质心 (c.m.) 平移能分布,并将其转化为 HCl 伴随碎片的转动态分布。这些分布与先前测量的 D(0) = 1334 ± 10 cm(-1) 的离解能一致,并显示出对最小化平移能量释放的 HCl 碎片转动能级的明显偏好。讨论了 2 + 1 REMPI 检测水碎片的有用性。