HeI ultraviolet photoelectron spectra of some thienyl polyethylenic dimethyl malonates compoundsf(1),(2),(3)(to see Fig.1)have been given in this paper. The assignment of the spectra are also done using the optimized MNDO molecular orbital calculation for each studied molecules. It is shown that the linear reduction of HOMO ionization energy (Ip) which is mainly antiboding in character of ethylenic group with the increment of ethylenic group number is fortunately the basis of the homologous lineax rule of this series of compounds. And it is also pointed out that weight of two -COOCH3 groups in the HoMO orbital is very small, that is to say, they can not be differentiated as the terminal or substituent.
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