An image of the heteroatom influence in acyclic polyenes

TL;DR

This paper develops a local theoretical framework to analyze how heteroatoms influence charge redistribution in acyclic polyenes, revealing the specific orbital interactions responsible for these effects.

Contribution

It introduces a novel local perspective on heteroatom effects in polyenes, decomposing charge redistribution into additive orbital interactions based on bond orbital interactions.

Findings

Charge redistribution decomposed into additive contributions.

Interactions depend on heteroatom positions within the polyene.

Local dipoles and interbond interactions explain heteroatom effects.

Abstract

The study is devoted to development of the theory of the heteroatom influence in acyclic polyenes from a local perspective. The charge redistribution due to introduction of heteroatom(s) (X) is decomposed into additive and meaningful contributions undergoing an extinction with growth of the substructure embraced. Each of these contributions, in turn, is traced back to specific additional interactions of bond orbitals (BOs) of C=C bonds of the parent hydrocarbon. The expansion starts with local and transferable dipoles of individual X=C (or C=X) bonds that are proportional to direct interactions of BOs within respective parent C=C bonds. Thereupon, populations transferred between first-neighbouring double bonds follow along with parallel and anti-parallel secondary (induced) dipoles of the latter. These contributions are determined by an interplay of two indirect interbond interactions of BOs and consequently depend on positions of heteroatom(s) inside the bonds concerned.