Strrcture determination of high-temperature species with a combined measurement system of a mass filter and a submillimeterwave spectrometer

1. 利用质谱可达m/z-400的四极杆质谱仪对一种高温物质进行鉴定，并与一种产生不稳定物质的系统相结合。我们开发了一个计算机程序，用它可以处理测量的质谱。马来酸酐和三甲基硼砂经热裂解形成短寿命分子。亚毫米光谱的测量我们测量了具有高自旋多重性的含金属分子的光谱。金属以支撑的方式从电极供应。对于含氯分子，像三氯化铝这样的低蒸气压分子适合作为溅射分子。在这种生产方法中，我们能够观察到CrCl (X^6SIGMA^+), FeCl (^6DELTA_<iota>), CrF (X^6SIGMA^+), CoF （X^3PHI）和NiF （^ 2i_ <3/2>, ^2SIGMA^+）的光谱。对于铬化合物，我们讨论了电子激发态对自旋-自旋和自旋-自旋相互作用的贡献。根据lamda型双倍分裂的旋转角动量依赖性，发现NiF的电子基态为^ 2i_ <3/2>。非常大的分裂表明电子激发的^2SIGMA^+态离基态不远。对于CoF，观察了OMEGA = 4自旋组分的跃迁，并确定了超精细相互作用常数。观察了NBr和NI自由基的谱，并从卤素原子的核四极矩讨论了键的离子性。在有氧和无氧条件下分别放电BBr_3，观察到短寿命硼化合物BBr和BBrO。

1. Identification of a high-tempoerature species with a mass filterA quadrupole mass spectrometer, which can measure the mass spectrum up to m/z-400, was combined with a system, in which unstable species were produced. We developed a computer program with which a measured mass spectrum could be processed. Maleic anhydride and trimethylboroxine was pyrolyzed to form short-lived molecules.2. Measurement of submillimeter spectraWe measured spectra of metal-containing molecules with high spin multiplicity. Metal was supplied from electrodes by way of supttering. For a chlorine containing molecule low vapor pressure molecule like aluminium trichloride was suitabl e as a sputtering molecule. In this method of production we were able to observe the spectra of CrCl (X^6SIGMA^+), FeCl (^6DELTA_<iota>), CrF (X^6SIGMA^+), CoF (X^3PHI) and NiF (^2II_<3/2>, ^2SIGMA^+). For chromium compounds we discussed the contribution of electronically excited states to spin-spin and spin-rotation interactions. For NiF the electronic ground state was found to be ^2II_<3/2> on the basis of the rotational angular momentum dependence of the LAMBDA-type doubling splitting. The very large splitting suggested that the electronically excited ^2SIGMA^+ state is not far distant from the ground state. For CoF the transition for the OMEGA = 4 spin component was observed and the hyperfine interaction constant was determined. The spectrum of NBr and NI radicals was observed and the ionicity of the bonding was discussed from the nuclear quadrupole moment of halogen atoms. Short lived boron compounds, BBr and BBrO,were observed by discharging BBr_3 with and without oxygen, respectively.