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Characterization of structural heterogeneity of liquid solutions and the pursuit of its nature have been challenging tasks to solution chemists. In the last decade, an emerging method called excess spectroscopy has found applications in this area. The method, combining the merits of molecular spectroscopy and excess thermodynamic functions, shows the ability to enhance the apparent resolution of spectra, provides abundant information concerning solution structures and intermolecular interactions. In this review, the thinking and mathematics of the method, as well as its developments, are presented first. Then, research progress related to the exploration of the method is thoroughly reviewed. The materials are classified into two parts, small-molecular solutions and ionic liquid solutions. Finally, potential challenges and the perspective for further development of the method are discussed.

Excess spectroscopy and its applications in the study of solution chemistry