The photoelectron spectra of the halomethanes

Abstract

The photoelectron bands associated with ionization from the formally non-bonding p orbitals of the halogen atoms in the halomethanes have been interpreted in terms of a pseudo one-electron hamiltonian. Account has been taken of interactions between the halogen atoms, of interactions between the halogen p orbitals and the σ-bonding orbitals, and of spin-orbit coupling. This model leads to a systematic assignment of all the bands of the chloro and bromomethanes, and gives a satisfactory account of the spin-orbit splittings in the bromomethanes.