The theory of double bond fixation in conjugated hydrocarbons
- 1 January 1966
- journal article
- research article
- Published by Taylor & Francis in Molecular Physics
- Vol. 11 (4) , 305-320
- https://doi.org/10.1080/00268976600101141
Abstract
A general method is given for treating the problem of bond fixation in conjugated hydrocarbons. Two effects are considered separately: first-order bond fixation from which bond-length-bond-order relationships may be derived, but which cannot lower the symmetry of the molecule; and second-order bond fixation which can lower the symmetry. It is shown that the most favourable distortion in the latter case is given by the lowest eigenvalue of the bond-bond polarizability matrix. The critical value for this eigenvalue appears to be about 1·8β -1. For values whose modulus is greater than this a distortion will occur which overcomes the σ-bond compression energy, and may lower the symmetry of the molecule.Keywords
This publication has 9 references indexed in Scilit:
- Ground States of Conjugated Molecules. I. Semiempirical SCF MO Treatment and Its Application to Aromatic HydrocarbonsThe Journal of Chemical Physics, 1965
- Bond length alternation in pentaleneMolecular Physics, 1961
- The alternation of bond lengths in large conjugated molecules. III. The cyclic polyenes C 18 H 18 , C 24 H 24 and C 30 H 30Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences, 1960
- Resonance and conjugation—II Factors determining bond lengths and heats of formationTetrahedron, 1960
- The alternation of bond lengths in long conjugated chain moleculesProceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences, 1959
- A Semi-empirical Theory of the Conjugated Systems I. General FormulationJournal of the Physics Society Japan, 1957
- Electron interaction in unsaturated hydrocarbonsTransactions of the Faraday Society, 1953
- The electronic structure of some polyenes and aromatic molecules. VII. Bonds of fractional order by the molecular orbital methodProceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences, 1939
- The electronic structure of some polyenes and aromatic molecules III—Bonds of fractional order by the pair methodProceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences, 1937