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首页> 外文期刊>The Journal of Chemical Physics >Examining transition metal hydrosulfides: The pure rotational spectrum of ZnSH ((X)over-tilde(2)A ')
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Examining transition metal hydrosulfides: The pure rotational spectrum of ZnSH ((X)over-tilde(2)A ')

机译：检查过渡金属氢硫化物：ZnSH（（x）过度波纹（2）A'）的纯旋转光谱

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The pure rotational spectrum of the ZnSH ((X) over tilde (2)A') radical has been measured using millimeter-wave direct absorption and Fourier transform microwave (FTMW) methods across the frequency range 18-468 GHz. This work is the first gas-phase detection of ZnSH by any spectroscopic technique. Spectra of the (ZnSH)-Zn-66, (ZnSH)-Zn-68, and (ZnSD)-Zn-64 isotopologues were also recorded. In the mm-wave study, ZnSH was synthesized in a DC discharge by the reaction of zinc vapor, generated by a Broidatype oven, with H2S; for FTMW measurements, the radical was made in a supersonic jet expansion by the same reactants but utilizing a discharge-assisted laser ablation source. Between 7 and 9 rotational transitions were recorded for each isotopologue. Asymmetry components with K-a = 0 through 6 were typically measured in the mm-wave region, each split into spin-rotation doublets. In the FTMW spectra, hyperfine interactions were also resolved, arising from the hydrogen or deuterium nuclear spins of I = 1/2 or I = 1, respectively. The data were analyzed using an asymmetric top Hamiltonian, and rotational, spin-rotation, and magnetic hyperfine parameters were determined for ZnSH, as well as the quadrupole coupling constant for ZnSD. The observed spectra clearly indicate that ZnSH has a bent geometry. The r(m)((1)) structure was determined to be r(Zn-S) = 2.213(5) angstrom, r(S-H) = 1.351(3) angstrom, and theta(Zn-S-H) = 90.6(1)degrees, suggesting that the bonding occurs primarily through sulfur p orbitals, analogous to H2S. The hyperfine constants indicate that the unpaired electron in ZnSH primarily resides on the zinc nucleus. Published by AIP Publishing.
机译：通过跨越频率范围18-468GHz的毫米波直接吸收和傅里叶变换微波（FTMW）方法，测量了ZnSH（（x）上的ZnSH（（x）的纯旋转光谱。这项工作是通过任何光谱技术的ZnSH的第一次气相检测。还记录了（ZnSH）-ZN-66，（ZnSH）-ZN-68和（ZnSD）-ZN-64同位素的光谱。在MM波研究中，通过锌蒸气的反应在DC放电中合成ZnSH，用H2S的葡萄周产生的锌蒸气反应;对于FTMW测量，通过相同的反应物在超音速喷射膨胀中进行自由基，而是利用排出辅助的激光烧蚀源。为每个同位素记录7至9的旋转过渡。通常在MM波区域中测量具有K-A = 0至6的不对称部件，每个都分成旋转旋转双板。在FTMW光谱中，分别也分解了高浓缩的相互作用，其分别由I = 1/2或i = 1的氢气或氘核旋转产生。使用不对称的顶部Hamiltonian分析数据，并确定用于ZnSH的旋转，旋转旋转和磁性高血清参数，以及用于ZnSD的四极耦合常数。观察到的光谱清楚地表明ZnSH具有弯曲的几何形状。将R（m）（（1））结构测定为R（Zn-S）= 2.213（5）埃，R（SH）= 1.351（3）埃埃斯特罗姆，θ（Zn-Sh）= 90.6（1暗示键合主要通过硫P轨道，类似于H2S发生。血清常数表明，ZnSH中的未配对电子主要在于锌核。通过AIP发布发布。

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