1. 1 6205334 無機光譜化學 Inorganic Spectroscopic Chemistry Time : Thursday 9:00 - 11:45Classroom : Chem 430 Textbooks : ˙ F.A. Cotton “Chemical Applications of Group Theory, 3rd ed.”, 1990, Wiley. ˙ E.A.V. Ebsworth, D.W.H. Rankin, S. Cradock “Structural Methods in Inorganic Chemistry, 2nd ed.”, 1991, CRC. ˙ R.S. Drago “Physical Methods for Chemists, 2nd ed.”, 1992, Saunders. ˙ A.K. Brisdon “Inorganic Spectroscopic Methods” 1998, Oxford. Contents :˙ UV-visible (electronic) spectroscopy Cotton Chapter 9 Ebsworth/Rankin/Cradock Chapter 6 Brisdon Chapter 4 ˙ IR/Raman (vibrational) spectroscopy Cotton Chapter 10 Ebsworth/Rankin/Cradock Chapter 5 Brisdon Chapter 2 ˙ Mass Spectrometry Ebsworth/Rankin/Cradock Chapter 9 Drago Chapter 16 Brisdon Chapter 5 ˙ NMR Spectroscopy Ebsworth/Rankin/Cradock Chapter 2 Drago Chapter 7, 8 Brisdon Chapter 3 ˙ ESR Spectroscopy Ebsworth/Rankin/Cradock Chapter 3 Drago Chapter 9 Brisdon Chapter 3 Grade :Mid-term 40% Final 40% Quiz 20%

2. 2 Introduction Determining structure ˙ contain any known compound? ˙ is it pure? ˙ what functional group it contains? ˙ what is its composition and molecular weight? ˙ how the functional groups linked together? ˙ what is molecular symmetry? ˙ what are the bond lengths and bond angles? ˙ what is its electronic structure?

3. 3 Some physical techniques in determining structure Fingerprint Group present Molecular symmetry Bond lengths and angles Electronic structure

4. 4 excited state electronic transition vibrational transition rotational transition ground state E = E electronic + E vibration + E rotation + E translation population distribution N upper ——— = exp(-  E/kT) k =1.381  10 -23 J/K N lower radiation E = h  = hc/ unit 1 nm = 10 -9 m 1 cm -1 = 11.98 J/mol = 2.86 cal/mol 1 eV = 96500 J/mol = 23060 cal/mol

5. 5 spectrum of electromagnetic radiation timescales associated with some spectroscopic techniques Energy of excited state Typical relaxation Typical Technique(Hz) time (seconds) linewidth (Hz) NMR (solution) 10 8 10 10 -1 ESR (solution) 10 10 10 -5 10 5 rotational spectroscopy (gas) 10 11 10 -4 10 4 vibrational spectroscopy (gas) 10 14 10 -8 10 8 electronic spectroscopy (solution) 10 16 10 -15 10 15 Mössbauer spectroscopy (solid) 10 19 10 -8 10 8 Nuclear energies Chemical energies Molecular energies Spin energies XRF ∣ Electronic ∣ ∣ Rotational ∣ Mössbauer XPS UPS ∣ Vibrational ∣ ESR NMR NQR GED XRD

6. 6 glossary of spectroscopic and structural techniques

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15. 15 Symmetry – group theory symmetry operation identityE inversioni reflection  rotationC rotation and reflectionS point group character table ex. What is the point group for [PtCl 4 ] 2- ? Cl Cl –– Pt –– Cl Cl symmetry element: E, C 4, C 2, i,  h,  v,  d, S 4 point group: D 4h

16. 16 character table of D 4h