On Relative Stabilities of Distinct Polyenes. An Extension of the Concept of Conjugated Paths

TL;DR

This paper extends a perturbative approach to analyze the relative stabilities of acyclic polyenes by including higher-order corrections and new conjugated path concepts, revealing the balance of stabilizing and destabilizing factors.

Contribution

It introduces new expressions for sixth-order energy corrections and expands the concept of conjugated paths to include destabilizing substructures in acyclic polyenes.

Findings

Higher-order terms are crucial for distinguishing similar isomers.

Conjugated paths of various lengths significantly influence stability.

New destabilizing fragments, called composite conjugated paths, are identified.

Abstract

The study continues the previous development [MATCH, 72 (2014) 39-73] of the perturbative approach to relative stabilities of pi-electron systems of conjugated hydrocarbons modeled as sets of weakly-interacting initially-double (C=C) bonds. Distinct isomers of acyclic hydrocarbons (polyenes) are now under focus. The relevant total pi-electron energies (E) are expressed in the form of power series containing members (E_(k)) of even orders (k=0,2,4,...) with respect to the averaged resonance parameter of initially-single (C-C) bonds. Terms to within the sixth order (k=6) inclusive are shown to be of importance for discrimination between similar isomers. In this connection, missing expressions for corrections E_(6) are originally derived. Conjugated paths of various lengths (i.e. linear chains consisting of C=C and C-C bonds alternately) are shown to be the most important (but not the only) fragments contributing to stabilization of any acyclic pi-electron system. Again, new types of fragments (substructures) are revealed (viz. the so-called composite conjugated paths) that contribute to destabilization of the system concerned. As a result, formation of the total energy of an acyclic pi-electron system is concluded to be governed by an interplay between stabilizing and destabilizing factors. Accordingly, the perturbative approach applied offers us an extension of the concept of conjugated paths. Particular isomers containing four, five and six C=C bonds are considered in a detail as examples.