PES lecture1 history

Photoelectron Spectroscopy : Photoelectron Spectroscopy Lecture 1: Development of Photoelectron Spectroscopy Photoionization “Koopmans’ Theorem” Brief Historical Overview Current Topics


Photoelectric Effect : Ionization occurs when matter interacts with light of sufficient energy (Heinrich Hertz, 1886) (Einstein, A. Ann. Phys. Leipzig 1905, 17, 132-148.) Ehn = electron kinetic energy + electron binding energy hn Photoelectric Effect Photoelectron spectroscopy uses this phenomenon to learn about the electronic structure of matter


General Overview of Spectroscopy : General Overview of Spectroscopy Spectroscopy uses interaction of electromagnetic radiation with matter to learn something about the matter. If electromagnetic radiation present is in resonance with the energy spacing between different states (electronic, vibrational, rotational, etc) of matter, radiation will be absorbed and transitions will occur. The radiation that is transmitted through the sample is measured, and spectrum can be reported as either transmittance or absorbance of radiation. Photoelectron spectroscopy is entirely different!


Photoelectron vs Other Spectroscopies : Photoelectron vs Other Spectroscopies Others Photon must be in resonance with transition energy Measure absorbance or transmittance of photons Scan photon energies Photoelectron Photon just needs enough energy to eject electron Measure kinetic energy of ejected electrons Monochromatic photon source


Why would a chemist care about ionizations anyway? : Why would a chemist care about ionizations anyway? Models for description of electronic structure are typically based on an orbital approximation. Tjalling C. Koopmans, "Ordering of Wave Functions and Eigenvalues to the Individual Electrons of an Atom." Physica 1933, 1, 104 Koopmans’ Theorem: “The negative of the energy of an occupied orbital from a theoretical calculation is equal to the vertical ionization energy due to the removal of an electron from that orbital.”


Ionization is still a transition between states : Ionization is still a transition between states Initial State: Neutral (or anion) Final State: Atom/Molecule/Anion after an electron is removed, plus the ejected electron M → M+ + e- More on this next time


Historical Timeline : Historical Timeline First spectrophotometer: 1850s First IR:1880s First crystallography: 1912 First NMR: 1938 First EPR: 1944 First PES: 1957


What took so long? : What took so long? Development of electron kinetic energy analyzers with sufficient resolution to be useful. Development of suitable sources of ionizing radiation – vacuum UV, soft X-ray Development of electron detectors Development of UHV technology


Slide9 : First Ionization Energies: cesium 3.89 eV (319 nm) ferrocene 7.90 eV (157 nm) water 12.61 eV (98 nm)


Kai Seigbahn: Development of X-ray Photoelectron Spectroscopy : Kai Seigbahn: Development of X-ray Photoelectron Spectroscopy Nobel Prize in Physics 1981 (His father, Manne Siegbahn, won the Nobel Prize in Physics in 1924 for the development of X-ray spectroscopy) C. Nordling E. Sokolowski and K. Siegbahn, Phys. Rev. 1957, 105, 1676.


Electron Spectroscopy for Chemical Analysis (ESCA) : Electron Spectroscopy for Chemical Analysis (ESCA) S. Hagström, C. Nordling and K. Siegbahn, Phys. Lett. 1964, 9, 235.


David Turner: Development of Ultraviolet Photoelectron Spectroscopy : David Turner: Development of Ultraviolet Photoelectron Spectroscopy D.W. Turner and M.I. Al Jobory, J. Chem. Phys. 1962, 37, 3007


Current Topics of Interest: high resolution : Current Topics of Interest: high resolution


Current Topics of Interest: angular dependence : Current Topics of Interest: angular dependence


Current Topics of Interest: variable photon studies : Current Topics of Interest: variable photon studies


Current Topics of Interest: applications to chemical problems : Current Topics of Interest: applications to chemical problems N N 9 8 7 6 5 Ionization Energy (eV) N N Ma—br—Mb Q- Adiabatic States - = (1/√2)(a - b) + = (1/√2)(a + b) Hab = <a|H|b> IE2 2Hab IE2 IE2 IE1 IE1


Summary : Summary PES is a fairly new technique, continuing to develop PES has unique features compared to other spectroscopies Valence spectroscopy: information on bonding Core spectroscopy: qualitative and quantitative analysis, “chemical shift”