INTERPRETATION OF THE HIGH-ENERGY BAND WITHIN THE PHOTOELECTRON-SPECTRA OF ALKANES BOTH IN TERMS OF APPROPRIATE ORBITALS AND ON THE BASIS OF CHEMICAL-STRUCTURE

Two generalized interpretations of the high-energy band (HEB) within the photoelectron spectra (PES) Of alkanes, usually referred to as the C-2s band, have been suggested. The quantum chemical one consists of attributing to the HEB Of any alkane (CnH2n+2) the chain of II similar orbitals eta(k) (k = 1...n), each of them containing mainly one 2s(c) AO and some contributions of another four orbitals from its nearest environment. The structure of each orbital eta(k) has been shown to be similar to that of the lowest totally symmetric hto of methane. The chemical interpretation of the same band involves relating it and the definite subspectrum of the full chemical graph of alkane, associated mainly with its C skeleton. The interrelation of these two complementary interpretations follows from the one-to-one correspondence between the orbitals eta(k) and the CH2(CH3) groups in alkane. (C) 1995 John Wiley and Sons, Inc.