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

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.

Nearest-Neighbour and Non-Nearest-Neighbour Non-Covalent Interactions between Substituents in the Aromatic Systems: Experimental and Theoretical Investigation of Functionally Substituted Benzophenones

“…The “centrepiece” approach has been described in detail in our previous papers [ 27 , 36 , 45 ]. The basic idea of the “centrepiece approach” approach is to select a relatively large “centrepiece molecule” (rather than the traditional summation of group contributions) with well-known thermodynamic properties that structurally most closely resembles the molecule of interest.…”

“…f Calculated by the G4 method using reaction: benzophenone + butane = acetone+ 2× toluene and using experimental (g)-values for the reaction participants [ 42 ]. g Results evaluated and recommended in our recent work [ 36 ].…”