Journal of Physical Chemistry A, Vol.103, No.35, 7069-7075, 1999
A generalized resonance model for substituted 1,4-benzoquinones
Resonance effects are known to affect vibrational spectra and electrochemical properties of substituted quinones. On the basis of the results of density functional calculations performed on several singly substituted 1,4-benzoquinones, we propose an extended resonance model which can account for the most prominent substituent effects onto the force constants of carbon-carbon and carbon-oxygen bonds. The calculations show that the two proposed resonance mechanisms are closely coupled. This interplay of the two effects renders a quantitative prediction of force constants of substituted 1,4-benzoquinone difficult. We nevertheless can give some simple rules which in many cases can give a good estimate for expected force constant changes upon substitution of 1,4-benzoquinone.