Merritt Jeremy M, Douberly Gary E, Stiles Paul L, Miller Roger E
Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, USA.
J Phys Chem A. 2007 Dec 13;111(49):12304-16. doi: 10.1021/jp074981e. Epub 2007 Sep 18.
Prereactive metal atom-HCN entrance channel complexes [M-HCN (M=Al, Ga, In)] have been stabilized in helium nanodroplets. Rotationally resolved infrared spectra are reported for the CH stretching vibration of the linear nitrogen-bound HCN-Ga and HCN-In complexes that show significant perturbation due to spin-orbit coupling of the 2Pi1/2 ground state with the 2Sigma1/2 state which are degenerate at long range. Six unresolved bands are also observed and assigned to the linear hydrogen-bound isomers of Al-HCN, Ga-HCN, and In-HCN corresponding to the fundamental CH stretching vibration and a combination band involving the CH stretch plus intermolecular stretch for each isomer. A nitrogen-bound HCN-Al complex is not observed, which is attributed to reaction, even at 0.37 K. This conclusion is supported by the observation of a weakly bound complex containing two HCN's and one Al atom which, from the analysis of its rotationally resolved zero-field and Stark spectra is assigned to a weakly bound complex of a HCNAl reaction product and a second HCN molecule. Theoretical calculations are presented to elucidate the reaction mechanisms and energetics of these metal atom reactions with HCN.
预反应性金属原子 - HCN 入口通道配合物[M - HCN（M = Al、Ga、In）]已在氦纳米液滴中得到稳定。报道了线性氮配位的 HCN - Ga 和 HCN - In 配合物 CH 伸缩振动的转动分辨红外光谱，这些光谱显示出由于 2Π1/2 基态与 2Σ1/2 态的自旋 - 轨道耦合而产生的显著扰动，这两个态在长程时是简并的。还观察到六个未分辨的谱带，并将其归属于 Al - HCN、Ga - HCN 和 In - HCN 的线性氢配位异构体，分别对应于基本的 CH 伸缩振动以及每个异构体涉及 CH 伸缩加分子间伸缩的一个组合带。未观察到氮配位的 HCN - Al 配合物，这归因于即使在 0.37 K 时也会发生反应。对含有两个 HCN 和一个 Al 原子的弱结合配合物的观察支持了这一结论，通过对其转动分辨的零场和斯塔克光谱分析，该配合物被归属于 HCN - Al 反应产物与第二个 HCN 分子形成的弱结合配合物。给出了理论计算以阐明这些金属原子与 HCN 反应的机理和能量学。
