An analysis of the magnetic hyperfine interactions in the microwave spectrum of NO–HF: Evidence of electron transfer
An analysis of the magnetic hyperfine interactions in the microwave spectrum of NO–HF: Evidence of electron transfer
复制标题
NO-HF 微波谱中磁超精细相互作用的分析：电子转移的证据
DOI：
--
复制
发表时间：
2001
期刊：
影响因子：
--
通讯作者：
B. Howard
中科院分区：
文献类型：
--
作者：
C. R. Dennis;C. J. Whitham;B. Howard
用傅里叶变换微波谱仪观测到了非HF络合物的四个转动跃迁的156个磁超精细跃迁。磁性超精细结构显示了由于氮、氢和氟原子核的相互作用。对精细结构和超精细结构的分析给出了a轴-NO角约为44°的弯曲几何结构，并表明面内NOπ*轨道相对于面外轨道具有很强的稳定性。H核和F核的费米接触相互作用具有相反的符号，与从头计算的比较表明，将较大的正相互作用分配给F核。结果揭示了由氢键引起的络合物中伙伴的电子结构扭曲的细节。
One hundred and fifty-six magetic hyperfine transitions belonging to four rotational transitions of the NO–HF complex have been observed using a Fourier transform microwave spectrometer. The magnetic hyperfine structure shows interactions due to the nitrogen, hydrogen, and fluorine nuclei. Analysis of both the fine and hyperfine structure gives a bent geometry with an a axis–NO angle of about 44° and indicates a strong stabilization of the in plane NO π* orbital with respect to the out of plane orbital. The Fermi contact interactions at the H and F nuclei have the opposite sign and comparison with ab initio calculations suggests assigning the larger positive interaction to the F nucleus. The results reveal details of the distortions of the electronic structure of the partners in the complex caused by the hydrogen bond.