?-BOND CONJUGATION IN POLYSILANES, A PES SCALED FREE-ELECTRON APPROACH FOR THE INTERPRETATION OF SKELETAL CLEAVAGE REACTION

Article abstract of DOI:10.1016/0022-328X(83)80238-1

The ?-orbital energies calculated by the simple free-electron model with a parametrization procedure recently by Von Szentpaly correlate very closely with the ?-band positions of the corresponding photoelectron spectra.For the ?-orbitals of three series of molecules: H(CH2)nH (n=2-4); H(SiH2)nH (n=2-5); Me(SiMe2)nMe (n=2-4) the FEMO model yields a standard error (SE) of 0.060 eV.Compared with HMO results (LCGO, LCBO and Sandorfy C) the correlation is significantly improved.The free-electron results are more accurate than those obtained using the PPP, CNDO/2, MINDO/3, SAMO and ab initio methods.The free-electron frontier orbital densities were successfully used to account for features of the skeletal cleavage reactions of polysilanes.