Seifert Nathan A, Hazrah Arsh S, Jäger Wolfgang
Department of Chemistry University of Alberta 11227 Saskatchewan Drive , Edmonton , Alberta Canada T6G 2G2.
J Phys Chem Lett. 2019 Jun 6;10(11):2836-2841. doi: 10.1021/acs.jpclett.9b00646. Epub 2019 May 16.
Using chirped-pulse Fourier transform microwave spectroscopy, we have experimentally identified the most abundant dimer of an alcohol analogue of naphthalene, 1-naphthol. The 1-naphthol dimer features a V-shaped, partially overlapping π-π stacked structure with no canonical hydrogen bonds between the subunits. This structural assignment is in contradiction to an earlier study of the 1-naphthol dimer using UV-IR dip double resonance spectroscopy in the O-H stretch region, which assigns a π-stacked but also canonically hydrogen-bonded structure. We use an improved theoretical analysis to resolve this discrepancy and show that the new, V-shaped structure is also consistent with the previously measured UV-IR data. These new computational and spectroscopic results shed light on the complicated nature of evaluating energetics and structures for larger, dispersion-bound systems.
利用啁啾脉冲傅里叶变换微波光谱技术，我们通过实验鉴定出了萘的醇类似物1-萘酚中最丰富的二聚体。1-萘酚二聚体具有V形、部分重叠的π-π堆积结构，亚基之间不存在典型的氢键。这一结构归属与早期在O-H伸缩区域使用紫外-红外双共振光谱对1-萘酚二聚体进行的研究相矛盾，早期研究认为其具有π堆积且存在典型氢键的结构。我们采用改进的理论分析来解决这一差异，并表明新的V形结构也与先前测得的紫外-红外数据一致。这些新的计算和光谱结果揭示了评估更大的色散束缚体系的能量学和结构的复杂性。
