Microwave spectra, geometries, and hyperfine constants of OCAgX (X = F, Cl, Br).
Microwave spectra, geometries, and hyperfine constants of OCAgX (X = F, Cl, Br).
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OCAgX（X = F、Cl、Br）的微波光谱、几何形状和超精细常数。
DOI：
10.1021/ic0105967
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发表时间：
2001
影响因子：
4.6
通讯作者：
M. Gerry
中科院分区：
文献类型：
--
作者：
N. Walker;M. Gerry
用脉冲射流腔傅里叶变换微波谱仪测量了OCAgX（X = F，Cl，Br）在5-22 GHz频率范围内的转动谱。金属原子通过激光烧蚀产生，并允许与CO和卤化物前体反应，然后在超音速氩气射流中稳定产物。这是OCAgF和OCAgBr的首次实验观测，也是OCAgCl的首次高分辨率光谱研究。这三种分子都是线性的。准确确定的旋转常数已被用来评估各种核间距，这被发现是一致的趋势建立OCAuX和OCCuX物种。C-O距离短，M-C距离明显长于其他含有金属-羰基键的分子。离心畸变常数和卤素核四极耦合常数的精确值也已确定。的耦合常数进行了比较，与以前的研究结果OCCuX和OCAuX，并用于推断分子的电子分布的趋势。从头计算已经进行，并采用预测的几何形状，振动频率，和Mulliken价轨道人口的各种物种。
A pulsed jet cavity Fourier transform microwave spectrometer has been used to measure the rotational spectra of OCAgX (X = F, Cl, Br) in the frequency range 5-22 GHz. Metal atoms were generated via laser ablation and were allowed to react with CO and a halide precursor, prior to stabilization of the products within a supersonic jet of argon. These are the first experimental observations of OCAgF and OCAgBr, and the first high resolution spectroscopic study of OCAgCl. All three molecules are linear. Accurately determined rotational constants have been used to evaluate the various internuclear distances, which are found to be consistent with trends established for OCAuX and OCCuX species. The C-O distances are short, and the M-C distances are significantly longer than those in other molecules containing a metal-carbonyl bond. Precise values of centrifugal distortion constants and halogen nuclear quadrupole coupling constants have also been determined. The coupling constants are compared with the results of previous studies of OCCuX and OCAuX and are used to infer trends in the electron distributions of the molecules. Ab initio calculations have been performed and employed to predict the geometries, vibrational frequencies, and Mulliken valence orbital populations of the various species.