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Bonding Nature in Photoelectron Spectra of the Molecules XY2
Author(s) -
Chen ErhHao,
Chang TseChiang
Publication year - 1998
Publication title -
journal of the chinese chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.329
H-Index - 45
eISSN - 2192-6549
pISSN - 0009-4536
DOI - 10.1002/jccs.199800006
Subject(s) - chemistry , molecular orbital diagram , molecular orbital , natural bond orbital , valence bond theory , localized molecular orbitals , lone pair , orbital hybridisation , molecular orbital theory , non bonding orbital , atomic orbital , molecule , atomic physics , molecular physics , computational chemistry , electron , physics , quantum mechanics , density functional theory , organic chemistry
The vibrational structures of photoelectron spectra can reveal the bonding nature of molecular orbitals. For diatomic molecules the bonding nature of molecular orbitals can be rationalized by the concepts of non‐bonding lone pair type and bonding type bond orbitals consisting of Lewis structures. For the simplest polyatomic molecules XY 2 the concepts of nonbonding lone pair type and bonding type bond orbitals and the method of expanding the canonical molecular orbitals into the bond orbitals are not quite appropriate. Two correlation diagrams, the distance correlation diagram and the angle correlation diagram, provide us with a better theoretical tool. The molecular orbital with the energy curve having positive slope in the distance correlation diagram (or angle correlation diagram) is identified as the R‐bonding (or 9‐bonding) orbital. The removal of an electron from the R‐bonding (or θ‐bonding) gives rise to vibrational excitation with decreasing frequency for the bond stretching (or bending) mode in the photoelectron spectra.