Combined High Resolution UV and Microwave Results: Structure of the Benzonitrile•Water Complex
Combined High Resolution UV and Microwave Results: Structure of the Benzonitrile•Water Complex
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高分辨率紫外和微波结果相结合：苯甲腈·水复合物的结构
DOI：
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发表时间：
1997
期刊：
影响因子：
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通讯作者：
H. Dreizler
中科院分区：
文献类型：
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作者：
R. Helm;H. Vogel;H. Neusser;V. Storm;D. Consalvo;H. Dreizler
摘要 采用高分辨率紫外（UV）和分子束傅里叶变换微波（MB FTMW）光谱对苯甲腈·水（BZNW）团簇进行了测量，以测量S0和S1态的团簇结构。 MW 实验提供了有关结构和基态 So 中 14N-核四极耦合的附加信息，UV 实验提供了有关 Si 动力学的附加信息。 BZNW 的旋转分辨亚多普勒紫外光谱是通过质量选择共振增强双光子电离测量的。这种紫外线技术首次应用于氢键团簇。通过相关自动旋转拟合从紫外光谱中获得旋转常数。使用包括核四极耦合的离心变形转子模型分析了MW谱。对簇内的水位置进行 r0 拟合。发现水及其氧几乎位于苯甲腈（BZN）平面上。对于 S0 (S1)，氧与邻位氢的距离为 r0 = 2.477(4) Å (2.457(2) Å)，与邻位碳-氢键的角度为 143.34(2)° (141.91(3)°)。 S1和S0的结构差异可以通过BZN分子的结构变化来解释。在 BZNW 簇中观察到线变宽，这表明 Si 在与极性溶剂成簇时衰减更快。
Abstract High resolution ultraviolet (UV) and molecular beam Fourier transform microwave (MB FTMW) spectroscopy of the benzonitrile·water (BZNW) cluster were performed to measure cluster structures in the S0 and S1 states. The MW experiments provide additional information on the structure and the 14N-nuclear quadrupole coupling in the ground state So, the UV experiments on the dynamics in Si. The rotationally resolved sub-Doppler UV spectra of BZNW were measured by mass-selective resonance-enhanced two-photon ionization. For the first time this UV technique has been applied to hydrogen-bonded clusters. From the UV spectra the rotational constants are obtained by Correlation Automated Rotational Fitting. The MW spectra were analyzed with the model of a centrifugally distorted rotor including nuclear quadrupole coupling. A r0 -fit of the water position within the cluster is performed. The water is found to be located with its oxygen nearly in the plane of benzonitrile (BZN). For S0 (S1), the distance of the oxygen to the ortho hydrogen is r0 = 2.477(4) Å (2.457(2) Å) and the angle to the ortho carbon-hydrogen bond 143.34(2)° (141.91(3)°). The structure differences in S1 and S0 can be explained by the structure changes of the BZN molecule. A line broadening, which points to a faster decay in Si upon clustering with the polar solvent, is observed for the BZNW cluster.