Archive | 2021
From gas phase to condensed phases: The mutable behavior of the Br2-water interaction
Abstract
Abstract In this work, we intend to present an ample view of the close interplay between the halogen-bond interaction with water and the structure of the solvent around it. Our interest in these systems initiated with Janda s and Apkarian s beautiful experiments [3] , [4] , [5] , [6] , these works made a significant contribution reaching a very detailed characterization of the electronic and vibrational properties of these systems. Herein, we will only refer to the visible and ultraviolet spectra determinations. The most extensive data set belongs to the case of bromine, where they recorded the UV–Vis spectra of single crystals of two different crystalline forms, the TS-I and CS-II phases, and amorphous solid water and aqueous solution. Our theory group has covered most of the possible systems where halogen molecules and water interact and characterized the most relevant aspects using different theoretical methodologies. With refined ab initio methods, it was possible to understand at the molecular level the observed spectroscopic signature of these systems. On the other hand, with semi-empirical refined models, it was possible to characterize the role thermal and dynamic effects have in the observed properties in condensed phase systems. This continuous line of research not only advanced the current picture on the changing behavior of halogen bond from the gas phase to condensed phases but also of the advantages and shortcomings of the theoretical tools used to study them.