Two-center three-electron bonding in ClNH3 revealed via helium droplet infrared laser Stark spectroscopy: Entrance channel complex along the Cl + NH3 → ClNH2 + H reaction
Two-center three-electron bonding in ClNH3 revealed via helium droplet infrared laser Stark spectroscopy: Entrance channel complex along the Cl + NH3 → ClNH2 + H reaction
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DOI：
10.1063/1.4947089
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发表时间：
2016-04-28
影响因子：
4.4
通讯作者：
Douberly, Gary E.
中科院分区：
文献类型：
--
作者：
Moradi, Christopher P.;Xie, Changjian;Douberly, Gary E.
Cl-2 的热解离解用于用单个 Cl 原子掺杂氦液滴。 NH3 依次添加到 Cl 掺杂液滴中，导致在取代反应 Cl + NH3 -> ClNH2 + H 的入口谷中形成复合物。NH 拉伸区域的红外 Stark 光谱揭示了 C-3v 对称顶部的对称和反对称振动。 NH3 的频移和偶极矩测量结果与含有相对较强的二中心三电子 (2c-3e) 键的 ClNH3 配合物一致。通过计算探索了 ClNH3 中 2c-3e 键合的性质，发现其与实验观察到的络合引起的蓝移一致。相互转化途径的计算揭示了该配合物形成的几乎无障碍途径，这与另外两种配合物 NH3Cl 和 Cl-HNH2 的实验光谱中的缺失一致，这两种配合物预计位于夺氢反应 Cl + NH3 -> HCl + NH2 的入口谷。由 AIP 出版社出版。
Pyrolytic dissociation of Cl-2 is employed to dope helium droplets with single Cl atoms. Sequential addition of NH3 to Cl-doped droplets leads to the formation of a complex residing in the entry valley to the substitution reaction Cl + NH3 -> ClNH2 + H. Infrared Stark spectroscopy in the NH stretching region reveals symmetric and antisymmetric vibrations of a C-3v symmetric top. Frequency shifts from NH3 and dipole moment measurements are consistent with a ClNH3 complex containing a relatively strong two-center three-electron (2c-3e) bond. The nature of the 2c-3e bonding in ClNH3 is explored computationally and found to be consistent with the complexation-induced blue shifts observed experimentally. Computations of interconversion pathways reveal nearly barrierless routes to the formation of this complex, consistent with the absence in experimental spectra of two other complexes, NH3Cl and Cl-HNH2, which are predicted in the entry valley to the hydrogen abstraction reaction Cl + NH3 -> HCl + NH2. Published by AIP Publishing.