Photoelectron spectroscopy of carbonyls. Lone-pair interactions in .alpha.-, .beta.-, .gamma.-, and .delta.-dicarbonyls

摘要: The ionization of the nonbonding electrons, n/sub +/, and -/, 73 dicarbonyls (38 ..cap alpha..-, 24 ..beta../sup 8 ..gamma..-, 3 delta-) has been surveyed experimentally (ultraviolet photoelectron spectroscopy) computationally (CNDO/s CNDO/2). Apart from certain readily rationalized exceptions, it is shown that energy split +//n/sub -/ events primarily determined by separation two carbonyl groups; splitting mechanism involves through-bond interaction with skeletal sigma orbitals; Franck-Condon band shapes I(n/sub +/) -/) are nature intermixed orbitals. A simple algorithm for +/)/I(n/sub splittings presented. 9 figures, 1 tables.