Thermochemistry in 21 st century – Quo Vadis? In silico assisted diagnostics of available thermochemical data

Abstract

Abstract Which comes first, experiment or theory? The answer is obvious – the experiment comes first. But how to be sure that the result of the experiment is reliable? Perhaps the crucial criterion is that the result should be consistent with the network of knowledge already available. In this study, we propose a step-by-step algorithm for quality diagnostics of thermochemical data on enthalpies of formation and enthalpies of phase transitions of organic compounds. The consistency of the data is studied and established using empirical structure-property correlations as well as using high-level quantum chemical calculations. The diagnostic algorithm is exemplarily demonstrated on a series of alkyl-substituted benzophenones for which conflicting thermochemical data were available.