Experimental Quantum Chemistry: A Hammett-inspired Fingerprinting of Substituent Effects
Artikel i vetenskaplig tidskrift, 2021

The quantum mechanically calculable Q descriptor is shown to be a potent quantifier of chemical reactivity in complex molecules – it shows a strong correlation to experimentally derived field effects in non-aromatic substrates and Hammett σm and σp parameters. Models for predicting substituent effects from Q are presented and applied, including on the elusive pentazolyl substituent. The presented approach enables fast computational estimation of substituent effects, and, in extension, medium-throughput screening of molecules and compound design. An experimental dataset is suggested as a candidate benchmark for aiding the general development and comparison of electronic structure analyses. It is here used to evaluate the experimental quantum chemistry (EQC) framework for chemical bonding analysis in larger molecules.

reactivity prediction

chemical bonding

linear free energy relationships

energy decomposition analysis

chemical descriptors


Francesco Sessa

Chalmers, Kemi och kemiteknik, Kemi och biokemi

Martina Olsson

Student vid Chalmers

Fredrik Söderberg

Chalmers, Fysik, Nano- och biofysik

Fang Wang

University of Rhode Island

Martin Rahm

Chalmers, Kemi och kemiteknik, Kemi och biokemi


1439-4235 (ISSN) 1439-7641 (eISSN)

Vol. 22 6 569-576


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