Abstract

The distribution of electronic spin in a series of linear odd-alternant polyene radicals is calculated using valence-bond, Hückel, and the ``extended'' Hartree—Fock methods. These theoretical results are compared with the spin distributions in a series of free radicals produced by irradiation of polyene acids, CH3 (CH=CH)m-1COOH, m=2–5, 7. The experimental spin distributions are deduced from the line shape of the ESR spectra of polycrystalline samples by making use of a method relating the second moments of the ESR spectra to the spin distribution. Experimental evidence is adduced for the presence of negative spin density on the ``unstarred'' atoms of these radicals. The relation between these results and the problem of bond alternation in long polyene radicals is discussed.

Keywords

PolyeneRadicalChemistrySpectral lineValence (chemistry)PhotochemistryComputational chemistryValence bond theoryElectron paramagnetic resonanceSpin densityNuclear magnetic resonanceOrganic chemistryMoleculeCondensed matter physicsMolecular orbitalPhysics

Affiliated Institutions

Related Publications

Publication Info

Year
1962
Type
article
Volume
37
Issue
2
Pages
361-367
Citations
46
Access
Closed

External Links

View on DOI.org

Social Impact

Altmetric
PlumX Metrics

Social media, news, blog, policy document mentions

Citation Metrics

46
OpenAlex

Cite This

Melvin W. Hanna, A. McLachlan, H. H. Dearman et al. (1962). Radiation Damage in Organic Crystals. III. Long Polyene Radicals. The Journal of Chemical Physics , 37 (2) , 361-367. https://doi.org/10.1063/1.1701327

Identifiers

DOI
10.1063/1.1701327