QUANTUM-MECHANICAL CHARACTERIZATION OF FUNCTIONAL-GROUPS FOR MOLECULAR SOLUTION THEORIES USING BADER FRAGMENTS

A method for characterising functional groups in organic molecules for use in group contribution molecular theories for liquid mixtures is p roposed. It uses a quantum mechanical criterion for electronic charge distribution based on the theory of atoms in molecules developed by Ba der, the distribution being established from ab initio quantum mechani cal computations. The method was developed by studying the main confor mers of linear alkanes from ethane to hexane, in addition to the follo wing linear esters; methyl, ethyl, propyl and butyl formate; methyl, e thyl and propyl acetate; methyl, ethyl and propyl propanoate; and meth yl and ethyl butanoate, The proposed criterion allows one not only to identify functional groups but also to account for proximity effects. It was validated by using the Nitta-Chao model to estimate thermodynam ic properties of the pure liquids studied (esters and alkanes) and the ir mixtures. The results were significantly better than those provided by earlier calculations for ester-alkane systems.