Molecular electronic spectroscopy: from often neglected fundamental principles to limitations of state‐of‐the‐art computational methods

Abstract

The creation of the first synthetic dyes not only stimulated the hunt for new colorants but also drove the search for rules correlating the constitution of organic compounds with their colour. Dye chemistry additionally facilitated the development of molecular electronic spectroscopy as well as theories of molecular electronic structure and electronic transitions. Powerful quantum chemical computational tools are now available for the prediction of the electronic structure and spectroscopic characteristics of organic compounds. Such methods are thus useful in designing new functional colorants and aiding interpretation of their properties. However, without a deep appreciation of the principles and assumptions behind the calculations, one runs the risk of misunderstanding what can be achieved as well as becoming confused about how the outputted electronic and vibronic transition data correspond to observed absorption spectra. This review therefore aims to cover fundamentals of electronic spectroscopy that are often overlooked and enable the dye chemist using modern computational methods to comprehend the subtle differences in the types of transition energy value that such software can generate. In addition, the limitations of these methods in predicting absorption maxima and intensities of real‐world colorants will be discussed in the context of physical influences on absorption band position and shape, for example from the perspective of different forms of the Franck–Condon principle. In essence, the goal of this review is to clarify, in terms that practical dye chemists will understand, what computational methods can predict and how valid these predictions are compared with reality.