W2013CHM2311 Part 4b Notes

Shi7 in requil between ab and ab ab ab ab ab

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Unformatted text preview: and Interorbital TransiHons – Theory and Experiment Molecular States (some) Measurement Methods H. Bock Ang. Chem. Int. Ed. 16, 613 (1997) One- electron MOs Photoelectron Spectrum of N2 2σg Ioniza0on poten0al (eV) 16 18 20 1πu 1σu 1σg 40 Orbital ionized N2 2σg 1πu 1σu VibraHonal Bond freq. (cm- 1) length (Å) 2330 1.0976 2175 1.116 1873 1.176 2373 1.075 VibraHonal Fine Structure. Shi7 in requil between AB and AB+. AB+ AB Ioniza7on Energy Ioniza7on Energy AB+ AB Franck- Condon ioniza7on takes place with no change in r(AB). Most probable state (vibra7onal) of AB+ is that with largest ψ2 at requil Large vibra7onal envelope observed for states where requi(AB+) ≠ requi(AB) VibraHonal Fine Structure. Shi7 in requil between AB and AB+. AB+ AB+ AB+ AB AB AB x- axis: internuclear separa0on; y- axis: energy SchemeHc PE Spectra Bands O2 – no sp mixing Fine Structure 2 σu πg 2 σg πu 1 σu Fine Structure πg πu 2σg 1σu 1 σg 1σg F2 – no sp mixing Bands Orbital Energy Bands 2σu Orbital Energy Orbital Energy N2 – sp mixing Fine Structure Discrepancy for O2, all bands doubled 1 σg πg πu 2σg 1 σu 2 σg 1πu 2 πg ↑↓ ↑↓ ↑ ↑↓ ↑↑ ↑↓ 2σu ↑↓ ↑↓ ↑↑ O2+ ↓ 1σu 1σg Different e- repulsion in these two states PE Spectra of Molecular Oxygen 1 σg O2 ↑↓ 1 σu 2 σg 1πu 2 πg ↑↓ ↑↓ ↑↓ ↑↑ 15 Molecular Orbital Theory: Heteronuclear Diatomic Molecules different kind of nuclei two...
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This note was uploaded on 03/28/2014 for the course CHM 2311 taught by Professor Richardson during the Winter '09 term at University of Ottawa.

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