《UPS-Lecture1_005》.pdf

Ultraviolet Photoelectron Spectroscopy (UPS)-1 Louis Scudiero /~scudiero; 5-2669 scudiero@ Koopmans’ Theorem The binding energy of an electron in state i is equal to the negative of the orbital energy of the ith state. I −ε i i (the ion is represented by (N-1) frozen orbitals) Koopmans’ theorem makes possible the identification of calculated orbital energies with ionization potentials. But it does not allow for electronic relaxation The ionization energy for the removal of electrons from different orbitals in a molecule is given by the energy difference between the initial state of the neutral molecule (in the ground state) and the final state that is the state of the ionized molecule. 1. Intra-molecular relaxation (relaxation energy for a free molecule) The N-1 electrons are rearranged around the hole, leading to lowering of the energy. 2. Extra-molecular Relaxation When a gas is chemisorbed on a surface the energy levels of the chemisorbed molecule are shifted relative to those of the free gas. Effects: Bonding (initial state) Relaxation (final state) or (polarization screening) The measured binding energy is always lower than the one calculated from Koopmans’ theorem. Example : O 1s in CO O 2s BE (expt) = 532.3 eV BE (expt) = 38.9 eV BE (Koopmans) = 562.4 eV BE (Koopmans) = 41.1 eV UV Commonly Used Lines (16.6 to 40.8 eV) Ionization sources are Ne I (16.6 eV), Ne II (26.8 eV) and He I (21.2 eV), He II (40.8 eV). These lines are produced by cold cathode capillary discharge. They represent resonance fluorescence produced when the gas is excited in the discharge and then decays back to its ground state. I -- lig