Nonlinear rotational spectroscopy reveals many-body interactions in water molecules
Nonlinear rotational spectroscopy reveals many-body interactions in water molecules
复制标题
非线性旋转光谱揭示水分子中的多体相互作用
DOI：
10.1073/pnas.2020941118
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发表时间：
2021
期刊：
影响因子：
--
通讯作者：
Nelson, Keith A.
中科院分区：
文献类型：
--
作者：
Zhang, Yaqing;Shi, Jiaojian;Li, Xian;Coy, Stephen L.;Field, Robert W.;Nelson, Keith A.
由于水分子在化学和生物学中的核心重要性，几十年来，水分子一直是光谱学研究的主题。水蒸气的旋转光谱学已经获得了有关孤立水分子以及水二聚体和水簇的结构和动力学的详细信息。近年来，人们发展了太赫兹非线性旋转光谱学来研究旋转能级有规则间隔的线性和对称顶分子的旋转动力学。然而，它还没有应用于水或其他具有不规则间距的低对称性分子。我们报告使用最近开发的二维（2D）太赫兹旋转光谱来观察以前无法观察到的高阶旋转相干和旋转跃迁之间的相关性。结果包括两量子（2Q）的峰值，其频率与两个不同分子的不同旋转跃迁的总和略有不同。这些结果直接揭示了以前未见过的亚稳水复合物的存在，其寿命为100 ps或更长。在不同的2Q频率上观察到几个这样的峰，表明配合物具有多个首选的双分子几何形状。我们的结果证明了在二维太赫兹光谱中测量的旋转相关性对分子相互作用和气相络合的敏感性。
Because of their central importance in chemistry and biology, water molecules have been the subject of decades of intense spectroscopic investigations. Rotational spectroscopy of water vapor has yielded detailed information about the structure and dynamics of isolated water molecules, as well as water dimers and clusters. Nonlinear rotational spectroscopy in the terahertz regime has been developed recently to investigate the rotational dynamics of linear and symmetric-top molecules whose rotational energy levels are regularly spaced. However, it has not been applied to water or other lower-symmetry molecules with irregularly spaced levels. We report the use of recently developed two-dimensional (2D) terahertz rotational spectroscopy to observe high-order rotational coherences and correlations between rotational transitions that were previously unobservable. The results include two-quantum (2Q) peaks at frequencies that are shifted slightly from the sums of distinct rotational transitions on two different molecules. These results directly reveal the presence of previously unseen metastable water complexes with lifetimes of 100 ps or longer. Several such peaks observed at distinct 2Q frequencies indicate that the complexes have multiple preferred bimolecular geometries. Our results demonstrate the sensitivity of rotational correlations measured in 2D terahertz spectroscopy to molecular interactions and complexation in the gas phase.
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影响因子：
4.4
作者：
HALL, RT;DOWLING, JM
通讯作者：
DOWLING, JM
DOI：
10.1073/pnas.1605631113
发表时间：
2016-06-21
影响因子：
11.1
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影响因子：
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作者：
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通讯作者：
K. Nelson
DOI：
10.1021/jp2043202
发表时间：
2010
期刊：
The journal of physical chemistry. A
影响因子：
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DOI：
10.1063/1.5108609
发表时间：
2019
期刊：
The Journal of chemical physics
影响因子：
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作者：
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通讯作者：
Y. Tanimura