Correlations between MO Eigenvectors and the Thermochemistry of Simple Organic Molecules, Related to Empirical Bond Additivity Schemes

Abstract

A bondingness term is further developed to aid in heat of formation (ΔfHº) calculations for C, N, O and S containing molecules. Bondingness originated from qualitative investigations into the antibonding effect in the occupied MOs of ethane. Previous work used a single parameter for bondingness to calculate ΔfHº in an alkane homologous series using an additivity scheme. This work modifies the bondingness algorithm and uses the term to parameterise a test group of 345 molecules consisting of 17 subgroups that include alkanes, alkenes, alkynes, alcohols, ethers, aldehydes, ketones, carboxylic acids, esters, amines, amides, diazenes, nitriles, nitroalkanes, nitrates, thiols and benzenoids. Comparing experimental with calculated ΔfHº values, a standard deviation for the residuals of 6.3 kJ mol 1 can be achieved using bondingness with a simple steric repulsion term (SSR) in a bond additivity scheme, and a standard deviation of 5.2 kJ mol 1 can be achieved using a Lennard-Jones potential. The method is compared with the group method of Pedley, which for a slightly smaller set of 338 molecules, a subset of the test set of 345 molecules, gives a standard deviation of 7.0 kJ mol 1.

Bondingness, along with SSR or a Lennard-Jones potential, is parameterised in the lowest level of ab initio (HF-SCF) or semiempirical quantum chemical calculations. It therefore may be useful in determining the ΔfHº values for the largest molecules that are amenable to quantum chemical calculation.

As part of our analysis we calculated the difference between the lowest energy conformer and the average energy of a mixture populated with higher energy conformers. This is the difference between the experimental ΔfHº value and the ΔfHº calculated for a single conformer. Example calculations which we have followed are given by Dale and Eliel et al.. Dale calculates the energy difference for molecules as large as hexane using relative energies based on the number of 1,4 gauche interactions. We have updated these values with constant increments ascertained by Klauda et al. as well as ab initio MP2 cc-pVDZ relative energies and have included calculations for heptane and octane.