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通讯:通过速度映射成像测定水二聚体(H2O)2 的键离解能(D0)。

Communication: determination of the bond dissociation energy (D0) of the water dimer, (H2O)2, by velocity map imaging.

机构信息

Department of Chemistry, University of Southern California, Los Angeles, California 90089-0482, USA.

出版信息

J Chem Phys. 2011 Jun 7;134(21):211101. doi: 10.1063/1.3598339.

Abstract

The bond dissociation energy (D(0)) of the water dimer is determined by using state-to-state vibrational predissociation measurements following excitation of the bound OH stretch fundamental of the donor unit of the dimer. Velocity map imaging and resonance-enhanced multiphoton ionization (REMPI) are used to determine pair-correlated product velocity and translational energy distributions. H(2)O fragments are detected in the ground vibrational (000) and the first excited bending (010) states by 2 + 1 REMPI via the C̃ (1)B(1) (000) ← X̃ (1)A(1) (000 and 010) transitions. The fragments' velocity and center-of-mass translational energy distributions are determined from images of selected rovibrational levels of H(2)O. An accurate value for D(0) is obtained by fitting both the structure in the images and the maximum velocity of the fragments. This value, D(0) = 1105 ± 10 cm(-1) (13.2 ± 0.12 kJ/mol), is in excellent agreement with the recent theoretical value of D(0) = 1103 ± 4 cm(-1) (13.2 ± 0.05 kJ∕mol) suggested as a benchmark by Shank et al. [J. Chem. Phys. 130, 144314 (2009)].

摘要

水二聚体的键离解能(D(0))是通过激发二聚体供体单元的束缚 OH 伸缩基频后进行态态振动预解离测量来确定的。速度图成像和共振增强多光子电离(REMPI)用于确定对关联产物速度和平移能分布。H(2)O 碎片通过 C̃ (1)B(1) (000) ← X̃ (1)A(1) (000 和 010)跃迁,通过 2 + 1 REMPI 在基态振动(000)和第一激发弯曲(010)态中被检测到。通过对 H(2)O 的选定转动振动能级的图像,可以确定碎片的速度和质心平移能分布。通过拟合图像中的结构和碎片的最大速度,可以得到 D(0)的准确值。这个值,D(0) = 1105 ± 10 cm(-1) (13.2 ± 0.12 kJ/mol),与 Shank 等人最近提出的作为基准的 D(0) = 1103 ± 4 cm(-1) (13.2 ± 0.05 kJ/mol)的理论值非常吻合。[J. Chem. Phys. 130, 144314 (2009)]。

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