Centre for Theoretical and Computational Chemistry (CTCC), Department of Chemistry, University of Oslo , P.O. Box 1033 Blindern, NO-0315 Oslo, Norway.
J Phys Chem A. 2013 Oct 10;117(40):10304-10. doi: 10.1021/jp407126x. Epub 2013 Sep 27.
The microwave spectrum of 4-isocyano-1-butyne (HC≡CCH2CH2N≡C) has been investigated in the 12.4-77.6 GHz spectral region. The spectra of two rotamers denoted ap and sc were assigned. ap has an antiperiplanar arrangement for the C-C-C-N chain of atoms, whereas sc has synclinal conformation for this link. The ground state spectrum and three vibrationally excited state spectra of the lowest torsional vibration were assigned for ap, while the ground vibrational state spectrum was assigned for sc. The C-C-C-N dihedral angle was found to be 64.5(30)° in sc and exactly 180° in ap. ap was determined to be 2.9(6) kJ/mol lower in energy than sc from relative intensity measurements. The microwave study has been augmented with ab initio and DFT calculations employing the CCSD(T), MP2, and B3LYP methods with the cc-pVTZ basis set. A Natural Bond Order analysis has also been performed. Most, but not all, of the quantum chemical predictions agree satisfactorily with the experimental results.
已在 12.4-77.6GHz 光谱区域研究了 4-异氰基-1-丁炔（HC≡CCH2CH2N≡C）的微波光谱。已分配了两种标记为 ap 和 sc 的旋转异构体的光谱。ap 中原子的 C-C-C-N 链呈反式排列，而 sc 中此键呈顺式构象。已分配了 ap 的基态光谱和三个最低扭转振动的振动激发态光谱，而 sc 的基态振动光谱已分配。在 sc 中，C-C-C-N 二面角被确定为 64.5(30)°，而在 ap 中正好为 180°。通过相对强度测量，ap 的能量比 sc 低 2.9(6)kJ/mol。微波研究已通过从头算和 DFT 计算得到补充，使用 CCSD(T)、MP2 和 B3LYP 方法以及 cc-pVTZ 基组。还进行了自然键轨道分析。大部分（但不是全部）量子化学预测与实验结果相符。
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