It is shown, by the MP2(fc)/6-31G*//HF/6-31G*+ZPE(HF/6-31G*) theoreti
cal model and subsequent use of homodesmic reactions, that the absolut
e proton affinities in disubstituted naphthalenes involving F and CN s
ubstituents satisfy the simple additivity rule, which was previously f
ound to hold in polysubstituted benzenes, the average absolute error b
eing close to 1 heal mol(-1), The origin of the remarkable additivity
of substituent effects in determining proton affinities in substituted
aromatics and the variations in the values are briefly discussed. (C)
1997 by John Wiley & Sons.