Experimental Quantum Chemistry: A Hammett-inspired Fingerprinting of Substituent Effects

• 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.

Ämnesord

NATURVETENSKAP  -- Fysik -- Annan fysik (hsv//swe)

NATURAL SCIENCES  -- Physical Sciences -- Other Physics Topics (hsv//eng)

NATURVETENSKAP  -- Kemi -- Teoretisk kemi (hsv//swe)

NATURAL SCIENCES  -- Chemical Sciences -- Theoretical Chemistry (hsv//eng)

NATURVETENSKAP  -- Kemi -- Organisk kemi (hsv//swe)

NATURAL SCIENCES  -- Chemical Sciences -- Organic Chemistry (hsv//eng)

Nyckelord

reactivity prediction

chemical bonding

linear free energy relationships

energy decomposition analysis

chemical descriptors

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