Departamento de Química Física y Química Inorgánica, Facultad de Ciencias-I.U. CINQUIMA, Universidad de Valladolid, Paseo de Belén, 7, 47011 Valladolid, Spain.
Dipartimento di Chimica ''Giacomo Ciamician'', Università di Bologna, Via Selmi, 2, 40126 Bologna, Italy.
Molecules. 2022 Apr 17;27(8):2584. doi: 10.3390/molecules27082584.
Weakly-bound intermolecular clusters constitute reductionist physical models for non-covalent interactions. Here we report the observation of the monomer, the dimer and the monohydrate of 2-adamantanol, a secondary alcohol with a bulky ten-carbon aliphatic skeleton. The molecular species were generated in a supersonic jet expansion and characterized using broadband chirped-pulse microwave spectroscopy in the 2-8 GHz frequency region. Two different - O-H···O hydrogen-bonded isomers were observed for the dimer of 2-adamantanol, while a single isomer was observed for the monomer and the monohydrate. The experimental rotational parameters were compared with molecular orbital calculations using density functional theory (B3LYP-D3(BJ), B2PLYP-D3(BJ), CAM-B3LYP-D3(BJ), ωB97XD), additionally providing energetic and electron density characterization. The shallow potential energy surface makes the dimer an interesting case study to benchmark dispersion-corrected computational methods and conformational search procedures.
弱束缚分子间簇合物构成非共价相互作用的简约物理模型。在这里，我们报告了金刚烷醇（一种带有庞大的十碳脂肪骨架的仲醇）的单体、二聚体和一水合物的观察结果。这些分子物种是在超音速射流膨胀中产生的，并在 2-8GHz 频率范围内使用宽带啁啾脉冲微波光谱进行了表征。对于金刚烷醇的二聚体，观察到了两种不同的-O-H···O 氢键异构形式，而对于单体和一水合物，仅观察到了一种异构形式。实验旋转参数与使用密度泛函理论（B3LYP-D3(BJ)、B2PLYP-D3(BJ)、CAM-B3LYP-D3(BJ)、ωB97XD）进行的分子轨道计算进行了比较，此外还提供了能量和电子密度特征。较浅的势能面使得二聚体成为一个有趣的案例研究，可以用于基准化分散校正计算方法和构象搜索程序。
