A technique called quantum topological molecular similarity (QTMS) was recently proposed [J. Chem. Inf. Comput. Sc., 2001, 41, 764] in order to construct a variety of medicinal, ecological and physical organic QSAR/QSPRs, based on modern ab initiowave functions of geometry optimised molecules, in combination with quantum chemical topology (QCT). The current abundance of computing power can be utilised to inject realistic descriptors into QSAR/QSPRs. In previous work [J. Chem. Soc., Perkin Trans. 2, 2002, 1231] it was proven that a set of Hammett constants (σp, σm, σ1and σp0 for a sizeable set of mono- and polysubstituted carboxylic acids can be replaced by QCT bond descriptors. Using QTMS and proper statistical validation we examined seven data sets in total. The first three sets (para-substituted phenols (σ-), substituted toluenes (σ) and bromophenethylamines (σ+)) corroborate that a wider class of Hammett constants can also be replaced by QCT descriptors. A fourth set (benzyl radicals) focuses on non-Hammett behaviour being superimposed on Hammett behaviour. QCT descriptors selectively correlate with Hammett behaviour. The QTMS analysis of the last three sets (toxicity of benzyl alcohols, Chromatographic capacity factors of chalcones and herbicidal activity of 5-chloro-2,3-dicyanopyrazines) screens for false positives. This test is successfully passed in that QCT descriptors fail when lipophilicity/hydrophobicity is in charge. Hence, overall, the discriminatory capacity of QCT descriptors is established, in detecting Hammett behaviour and specifically replacing the Hammett constants by more modern and non-empirical descriptors. © The Royal Society of Chemistry 2005.