物理化学学报 >> 2016, Vol. 32 >> Issue (1): 239-248.doi: 10.3866/PKU.WHXB201511241

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超额光谱及其研究进展

周瑜1,徐静1,王楠楠2,尉志武1,*()   

  1. 1 清华大学化学系,生命有机磷化学及化学生物学教育部重点实验室,北京 100084
    2 国防科学技术大学航天科学与工程学院,新型陶瓷纤维及其复合材料重点实验室,长沙 410073
  • 收稿日期:2015-10-19 发布日期:2016-01-13
  • 通讯作者: 尉志武 E-mail:yuzhw@mail.tsinghua.edu.cn
  • 基金资助:
    国家自然科学基金(21133009, 21473099)

Excess Spectroscopy: Concept and Applications

Yu ZHOU1,Jing XU1,Nan-Nan WANG2,Zhi-Wu YU1,*()   

  1. 1 Key Laboratory of Bioorganic Phosphorous Chemistry and Chemical Biology (Ministry of Education), Department of Chemistry, Tsinghua University, Beijing 100084, P. R. China
    2 Key Laboratory of Science and Technology on Advanced Ceramic Fibers and Composites, College of Aerospace Science and Engineering, National University of Defense Technology
  • Received:2015-10-19 Published:2016-01-13
  • Contact: Zhi-Wu YU E-mail:yuzhw@mail.tsinghua.edu.cn
  • Supported by:
    the National Natural Science Foundation of China(21133009, 21473099)

摘要:

超额光谱是借助于热力学中超额函数的概念提出的,是经典热力学函数的补充,它可以提供丰富的分子间相互作用的信息。本文首先介绍了超额光谱的概念和测定方法。然后介绍了超额光谱的用途:提高谱图的表观分辨率、判断体系的非理想性、判断分子间选择性相互作用的优先性、判断二态性以及稳定缔合体的存在和提供分子电荷分布的信息等。其后介绍了超额光谱方法学的若干新进展:超额拉曼光谱、超额偏摩尔红外光谱和固体假二元超额光谱。最后,介绍了超额光谱在几个方面的最新应用:离子液体和分子溶剂体系中的氢键、苯衍生物和二甲基亚砜(DMSO)中的卤键、无机阴阳离子和水的相互作用。综上,超额光谱可以帮助我们得到更加丰富的分子间相互作用的信息,为该领域的研究打开了一扇新窗户。

关键词: 超额光谱, 衰减全反射红外光谱, 氢键, 卤键, 分子间相互作用, 聚集体, 物种指认

Abstract:

Excess spectroscopy was proposed following the idea of excess thermodynamic functions. It is complementary to classical excess functions because it provides rich information on molecular interactions. In this review, we introduce in detail the concept of excess spectroscopy and the measurement of excess spectra for the case of infrared spectroscopy. We then describe the merits of using excess spectroscopy to enhance apparent spectral resolution, judge the non-ideality of mixtures, determine the selectivity of molecular interactions, identify distinct species or clusters in solutions, and provide information related to charge distributions in molecules. Following this, we review the progress in methodology where excess spectroscopy is extended to partial molar excess spectroscopy and Raman spectroscopy. The extension of binary mixtures to pseudo binary mixtures and/or liquid samples to solid samples is also described. Finally, we discuss several recent applications of excess spectroscopy in the study of hydrogen-bonding interactions in ionic liquid-molecular solvent systems, halogen-bonding interactions in benzene derivative-dimethylsulfoxide (DMSO) mixtures, and interactions between inorganic cations/anions and water molecules. Clearly, excess spectroscopy has opened a new window through which we can view rich information about molecular interactions.

Key words: Excess spectra, ATR-IR, Hydrogen bond, Halogen bond, Molecular interaction, Cluster, Species identification

MSC2000: 

  • O645