Experimental Quantum Chemistry: A Hammett-inspired Fingerprinting of Substituent Effects
Journal article, 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.

energy decomposition analysis

chemical bonding

chemical descriptors

linear free energy relationships

reactivity prediction

Author

Francesco Sessa

Chalmers, Chemistry and Chemical Engineering, Chemistry and Biochemistry

Martina Olsson

Chalmers, Physics, Materials Physics

Fredrik Söderberg

Chalmers, Physics, Nano and Biophysics

Fang Wang

University of Rhode Island

Martin Rahm

Chalmers, Chemistry and Chemical Engineering, Chemistry and Biochemistry

ChemPhysChem

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

Vol. 22 6 569-576

Subject Categories

Other Physics Topics

Theoretical Chemistry

Organic Chemistry

DOI

10.1002/cphc.202001053

PubMed

33502056

More information

Latest update

3/18/2021