Contributions from inner and outer shell electron energies to reaction heats for C1, C2, and C3 hydrocarbons

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Abstract
The expectation energy values EK, Vee, Vnn, Ven, and ET have been calculated for H2 and the C1, C2, and C3 hydrocarbons using a (9,5) basis set and the experimental geometries. Treating the theoretical reaction heat, ΔET, as the resultant of the nuclear repulsion term, ΔVnn, and the net electron energy term, ΔEelec = ΔEK + ΔVee + ΔVen, the contribution of inner and outer shell electron energies to ΔEelec, and hence to ΔET, has been calculated for a large number of hydrocarbon reactions by evaluating the Coulson–Neilson energies ηi, where Σηi = Eelec. For the vast majority of reactions, 67/84, the change in inner shell electron energy, (Σηi)inner, accounts for more than 10% of ΔEelec, in many cases being as high as 20–35%. Furthermore, in addition to these cases in which the change in inner shell electron energy serves to augment (significantly) the change in outer shell electron energy, there are other cases in which the change in inner shell electron energy either exceeds in magnitude the change in outer shell energy, or is even opposite in sign, indicative of inner and outer shell electrons acting contrariwise. Inner shell electron energies contribute to the reaction heats because they are structure dependent, like the more familiar orbital energies ε, but the dependence is of a different kind.

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