The role of intensities in determining characteristics of spectroscopic networks
The role of intensities in determining characteristics of spectroscopic networks
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DOI：
10.1016/j.molstruc.2011.10.057
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发表时间：
2012-02-15
影响因子：
3.8
通讯作者：
Csaszar, Attila G.
中科院分区：
文献类型：
--
作者：
Furtenbacher, Tibor;Csaszar, Attila G.
光谱网络 (SN) 是大型、有限、加权、无向、有根图，其中顶点是离散能级，边是过渡，权重是过渡强度。虽然第一原理 SN 根据定义是“确定性的”，但如果在构建这些 SN 期间采用现实的过渡强度截止，则会引入一定的随机性（“随机性”）。实验自然会构建随机图。以水分子的 (HDO)-O-16 同位素异体体为例，显示了强度（在本例中为单光子吸收强度）如何决定 SN 的结构以及程度分布和边缘密度。实际计算的 SN 的度分布可以描述为无标度，具有常见且众所周知的后果。基于测量和分配的跃迁的实验 SN 也被证明是无标度的。高分辨率分子光谱的图论视图为提高包含光谱数据的信息系统的准确性和鲁棒性提供了几种新的想法。例如，研究表明，大多数旋转振动能级至少涉及一些相对较强的跃迁，这表明可以从测量中推断出几乎完全覆盖的实验质量能级。 (C) 2011 Elsevier B.V. 保留所有权利。
Spectroscopic networks (SNs) are large, finite, weighted, undirected, rooted graphs, where the vertices are discrete energy levels, the edges are transitions, and the weights are transition intensities. While first-principles SNs are "deterministic" by definition, if a realistic transition intensity cut-off is employed during the construction of these SNs, a certain randomness ("stochasticity") is introduced. Experiments naturally build random graphs. It is shown on the example of the (HDO)-O-16 isotopologue of the water molecule how intensities, in the present case one-photon absorption intensities, determine the structure as well as the degree distribution and edge density of SNs. The degree distribution of realistic computed SNs can be described as scale free, with the usual and well known consequences. Experimental SNs, based on measured and assigned transitions, also turn out to be scale free. The graph-theoretical view of high-resolution molecular spectra offers several new ideas for improving the accuracy and robustness of information systems containing spectroscopic data. For example, it is shown that most all rotational vibrational energy levels are involved in at least a few relatively strong transitions suggesting that an almost complete coverage of experimental quality energy levels can be deduced from measurements. (C) 2011 Elsevier B.V. All rights reserved.