Linear free energy relationships in kinetic analyses. Applications of quantum chemistry

Matthew Neurock, Michael T. Klein

Research output: Contribution to journalConference articlepeer-review

3 Scopus citations


Linear free energy relationships are a useful organizational device for the summary of experimental data in complex reaction systems. These relationships provide a direct link between structure-engendered reactivity properties and experimental kinetic parameters, thus allowing the reduction of many kinetic parameters into a series of slopes and intercepts. In this work, the reactivity indices that provided the basis for such correlations were determined from quantum chemical calculations. Simple EHT and MNDO calculations allowed for very good correlations of kinetic and adsorption data. The properties for over 150 components including neutral components, carbenium ions and free radicals were faithfully computed by MNDO and EHT techniques. LFER's provide a means for organizing existing data and testing their chemical significance. They also provide a basis for the predicting the kinetics for many experimentally unstudied systems. This is a first step toward the realization of detailed molecular reaction simulations which internally call quantum chemical programs to compute intrinsic reactivity.

Original languageEnglish (US)
Pages (from-to)631-640
Number of pages10
JournalAmerican Chemical Society, Division of Petroleum Chemistry, Preprints
Issue number2
StatePublished - Mar 1 1992
EventSymposium on Molecular Modeling of Petroleum Processes and Catalysis - San Francisco, CA, USA
Duration: Apr 5 1992Apr 10 1992


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