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Ionization

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Why are ionizations interesting

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Slide1 :

Slide2 : e- e- e- e- Einstein Photoelectric Effect Ann. Phys. Leipzig 1905, 17, 132-148 Nobel Prize in Physics, 1921

Slide3 : e- e- e- Einstein Photoelectric Effect Ehv - Ee- = Ionization Energy hv e-

Slide4 : “The importance of ionization energy lies in the close correlation found between electron configuration (a microscopic property) and chemical behavior (a macroscopic property). ...The chemical properties of any atom or molecule are related to the configuration of the atom's or molecule’s valence electrons, and the stability of these electrons is reflected directly in the ... ionization energies.” ...provide well-defined, precise benchmarks for computational methods. ...are important quantities in thermodynamic cycles. (above from Raymond Chang, "General Chemistry") Why Ionization Energies?

Slide5 : AUFBAU PRINCIPLE Electrons tend to occupy the most stable orbitals. KOOPMANS’ THEOREM Ionization energies correspond to orbital energies. BOND PRINCIPLES i.e. The sigma bond between two atoms is stronger than the pi bond. ELECTRONEGATIVITY PRINCIPLES i.e. Fluorine is highly electronegative and attracts electron density. REACTIVITY PRINCIPLES i.e. Protonation occurs at the atom with the most unstable electron density. i.e. Chemical oxidation removes the electron from the highest occupied orbital. Ionizations Provide Experimental Basis for Common Chemistry Principles

Slide6 : Fundamental Chemical Understanding 3. What is the energy profile of the process? The Molecular Structure View

Slide7 : Fundamental Chemical Understanding The Molecular Structure View 1. Where do atoms begin and where do they end? 2. What is the mechanism of the process? 3. What is the energy profile of the process? Reaction coordinate Energy The Electronic Structure View 1. Where do electrons begin and where do they end?

Slide8 : Chemistry is About Movement of Electrons Electrochemistry Energy Storage Energy Conversion Biology

Slide9 : 2. Electron Transfer Processes: [Cr(OH2)6] 2+ + [CoCl(NH3)5] 2+ Chemistry is About Movement of Electrons Molecular Electronics Energy Conversion Photochemistry Biology

Slide10 : Chemistry is About Movement of Electrons 3. Bond Making / Bond Breaking Processes: C C H Br + Synthesis Catalysis Acid / Base Chemistry Etc. Etc.

Slide11 : Chemistry is About Movement of Electrons 4. Electronic Transitions: Spectroscopy Photochemistry Optoelectronics Photosynthesis

Slide12 : Core Ionizations are Element Specific ..and Dependent Upon Environment

Slide13 : Photoelectron Spectroscopy is a Huge Field: Search of J. Am. Chem. Soc. ASAP articles, current + four years for “photoelectron” yielded 444 articles!

Slide14 : Wide Range of Applications

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