Band designation in Chapter 5

3. Band designation in Chapter 5

8. Fermi Resonance (2 vib levels)

11. Normal Modes 3N-6 3N-5 (Linear)

20. (3.1) (stationary states) (3.9) (3.10)

23. SPECTROSCOPY OVERVIEW upper state denoted by single apostrophe lower “ “ “ double “ ro-vibronic transition (electronic) Vibrational transition Rotational transition

24. v’ J’ v’’ J’’

26. 4 g

27. *

28. intersystem crossing nonradiative decay absorption fluorescence phosphorescence S = 0 S = 1 or S = 1 S = 0 Franck-Cendon factor Hönl-London factor (1927)

29. Terminology Vibrational transitions 2 2 hot band Overtone (due to anharmonicity) 1 1 Combination band fundamental + 0 0 v1 Normal modes v1 v2

31. Rotation – Vibration bands (p. 90) 13 Transition v’ , J’ – v’’ , J’’ upper lower emission absorption J’ = J’’ + 1 R – branch J’ = J’’ Q – branch J’ = J’’ – 1 P – branch J’ = J” + 1 J’ = J” v’ J’ = J” - 1 Q R P J” v” Δv = ± 1 ΔJ = 0 (some cases) ±1 Δv = arbitrary for different e states

33. I2 v1= 213.2 cm-1 T = 300 K (= 208.7 cm-1) vibrational population

34. Rotational population

37. coupling of degenerate vibration N2O doubling to rotation

40. 2

41. Pure sine wave Finite life time (3.48) quantum life time Natural line width collision life time Lorentz line width V V + W (3.52) Quantum veresion

42. 4 (3.79) (Frequency shift) (3.48) (3.51) (collision frequency)

43. 5 Doppler + Lorentz In dimensionless units

49. 18