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.

energy decomposition analysis

chemical bonding

chemical descriptors

linear free energy relationships

reactivity prediction

Författare

Francesco Sessa

Chalmers, Kemi och kemiteknik, Kemi och biokemi

Martina Olsson

Chalmers, Fysik, Materialfysik

Fredrik Söderberg

Chalmers, Fysik, Nano- och biofysik

Fang Wang

University of Rhode Island

Martin Rahm

Chalmers, Kemi och kemiteknik, Kemi och biokemi

ChemPhysChem

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

Vol. 22 6 569-576

Ämneskategorier

Annan fysik

Teoretisk kemi

Organisk kemi

DOI

10.1002/cphc.202001053

PubMed

33502056

Mer information

Senast uppdaterat

2021-03-18