  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.
