Analysis of the Intermolecular Dynamics of Open-shell Radical Complexes

开壳层自由基配合物的分子间动力学分析

• 批准号: 07454148
• 负责人: ENDO Yasuki
• 金额: $ 4.8万
• 依托单位: The University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1996
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07454148/
• 关键词: Open-shell molecule; Molecular complex; Fourier-transform microwave spectroscopy; Double resonance spectroscopy; Molecular ion complex; Intermolecular interaction; Molecular orbital method; 分子軌道法; 分子錯体; フリーラジカル; マイクロ波分光; 2重共鳴分光; 分子内大振幅運動

Compared to the closed shell molecular complexes, molecular complexes containing open shell species species or ionic have little been studied by high-resolution spectroscopic methods. The present project intended to investigate these species by using Fourier-transform microwave spectroscopy or mm-wave/cm-wave double resonance spectroscopy in order to elucidate intermolecular interactions. Specific interest lies in the roles of the unpaired electron in the open shell species and the charge in the ionic species how they contribute to the intermolecular dynamics.During the period of present research project, we observed rotational spectra of Ne-OH,Kr-OH,Ar-SH,H_2O-OH,H_2O-SH,Ar-HCO^+, and Kr-HCO^+ for the first time. Results of Ne-OH and Kr-OH and Kr-OH were analyzed by a method previously applied to the Ar-OH system, considering large amplitude motion of the OH moiety and the couplings of the spin and orbital angular momenta of the unpaired electron. The intermolecular interaction potent … More ials were compared with that of Ar-OH,and their differences were explained by considering the polarizabilities of the rage-gas atoms. Similar analysis has been applied to the analysis of Ar-SH.The resulting intermolecular potential for Ar-SH i quite different from those of Rg-OH systems : anisotropy around OH is much smaller than those of Rg-OH,undergoing large amplitude motion with larger amplitude.Spectroscopic detections of H_2O-OH and H_2S-SH are important as these complexes are closely related to the understanding of the hydrogen exchange reactions. The observed spectrum of H_2O-OH was analyzed as the system is a doublet asymmetric rotor with the orbital angular momentum in OH completely quenched. The two hydrogen atoms in H_2O showed appreciable magnetic hyperfine splittings suggesting some delocalization of the unpaired electron on the OH radical. Theintermolecular distance was explained as the two constituents were bonded by the hydrogen bonding with OH proton to be proton donor. The spectrum of H_2S-SH showed many anomaly and detailed analysis is still under way.The ionic complexes Ar-HCO^+ and Kr-HCO^+ were studied in detail including their various isotopomers, yielding precise determination of their molecular structure. The Rg-H distances thus obtained were much smaller than those of neutral complexes. They were well explained by considering a rather simple electrostatic model. The present results also agrees with large scale ab initio calculations including their intermolecular potentials indirectly estimated from the present experimental data.In order to understand intermolecular, we performed ad initio molecular orbital calculations for these systems. We obtained fair agreements for H_2O-OH and ion complexes. We expect that molecular orbital calculations will help further understanding of the intermolecular intermolecular for such systems. Less

与封闭的壳分子络合物相比，高分辨率光谱法几乎没有研究含有开放壳物种或离子的分子复合物。本项目旨在通过使用傅立叶转换微波光谱或MM-WAVE/CM波双共振光谱来研究这些物种，以阐明分子间相互作用。具体的兴趣在于未配对电子在开放壳物种中的作用以及在离子物种中的电荷如何对分子间动力学做出贡献。在本研究项目的时期，我们观察到了NE-OH，KR-OH，KR-OH，AR-SH，H_2O-OH，H_2O-OH，H_2O-SH，H_2O-SH，AR-HCO^+的第一次旋转光​​谱。通过以前应用于AR-OH系统的方法分析了NE-OH和KR-OH和KR-OH的结果，考虑到OH部分的大幅度运动以及未配对电子的自旋和轨道角动量的大幅度运动。分子间的相互作用潜力…将更多的IL与AR-OH进行了比较，并且通过考虑rage-Gas原子的极化能力来解释它们的差异。类似的分析已应用于AR-SH的分析。AR-SH I与RG-OH系统的分子间潜力完全不同：OH周围的各向异性与RG-OH的各向异性相比要小得多，而RG-OH进行了较大的放大器运动，并具有较大的放大器运动。SpectRoscopic检测H_2O-OH和H_2S-SHS-SHS-SHEMPERTION与这些复合物的反应很重要。分析了观察到的H_2O-OH的光谱，因为系统是双重不对称的转子，其轨道角动量在OH中完全淬火。 H_2O中的两个氢原子表现出可欣赏的磁性超细分裂，表明在OH激进分子上未配对电子的迁移率进行了定位。当两个构建体与OH质子键合为质子供体时，对间分子的距离进行了解释。 H_2S-SH的频谱显示出许多异常，并且仍在进行详细的分析中。详细研究了离子复合物AR-HCO^+和KR-HCO^+，包括它们的各种同位素体，可以准确确定其分子结构。这样获得的RG-H距离比中性复合物的距离要小得多。通过考虑一个相当简单的静电模型来很好地解释它们。目前的结果还与大规模的从头算计算一致，包括从本实验数据中间接估计的分子间电位。为了理解分子间，我们对这些系统进行了AD Initio Molecular Molecular Orbital计算。我们获得了H_2O-OH和离子综合体的公平协议。我们预计分子轨道计算将有助于进一步了解此类系统的分子间分子间。较少的

项目成果

Y.Kasai: "Laboratory detection of the C_5N radical by Fourier-transform microwave spectroscopy" Astrophys.J.(印刷中). (1997)

Y.Kasai：“通过傅里叶变换微波光谱法对 C_5N 自由基进行实验室检测”Astrophys.J（出版中）。

H.Kohguchi, Y.Ohshima, and Y.Endo: "Laser-induced-fluorescence spectra and obervation of quantum beats in the A^2PI_i-X^2PI_i transition of the HCCS radical" Chem.Phys.Lett.254. 397-402 (1996)

H.Kohguchi、Y.Ohshima 和 Y.Endo：“激光诱导荧光光谱和 HCCS 自由基 A^2PI_i-X^2PI_i 跃迁中量子拍的观察”Chem.Phys.Lett.254。

H.Kohguchi: "Laser-induced fluorescence spectroscopy of the C^2Σ^+-X^2TT_<1/2> bend systen of jet-cooled CCN" J.Chem.Phys.(印刷中). (1997)

H.Kohguchi：“喷射冷却 CCN 的 C^2Σ^+-X^2TT_<1/2> 弯曲系统的激光诱导荧光光谱”J.Chem.Phys（出版中）。

Y. Kasai: "Pure rotational spectrum of FeCO" J. Chem. Phys.103. 90-95 (1995)

Y. Kasai：“FeCO 的纯旋转光谱”J. Chem。

Y.Kasai, Y.Sumiyoshi, Y.Endo, and K.Kawaguchi: "Laboratory datection of the C_5N radical by Fourier-transfrom microwave spectroscopy" Astrophys.J.(in press). (1997)

Y.Kasai、Y.Sumiyoshi、Y.Endo 和 K.Kawaguchi：“通过微波光谱的傅里叶变换对 C_5N 自由基进行实验室测定”Astrophys.J.（出版中）。