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Lecture 25 - Spectroscopy

# Lecture 25 - Spectroscopy - Chapter 14 Spectroscopy...

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Chapter 14: Spectroscopy Homework: 2, 4, 6, 8, 10, 12, 24, 26, 28, 30, 32, 34, 36, 38, 39, 42, 47, 60, 67, 68, 74, 76, 80, 82, 84 h ν π π *

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Spectral Line Width Gas phase Solution π π * 1 1 Z t = = Δ τ t h E Δ Δ π 4 Z 1 10 8 s -1 (gas) τ = 10 ns Z 1 10 12 s -1 (soln) τ = 1 ps π 4 h t E Δ Δ
Excited State Lifetime vs ν ν h E E E m n = = Δ W mn = aborption rate A nm = excited state lifetime B mn = Einstein coefficient N m = # molecules in m ρ ( ν ) = radiation density ) ( ν ρ m mn mn N B W = nm n A N ) ( ν ρ n nm nm N B W = absorption stimulated emission spontaneous emission nm n nm n mn m A N B N B N + = ) ( ) ( ν ρ ν ρ 1 1 ) ( / = kT h nm nm e B A ν ν ρ 1 1 8 ) ( / 3 3 = kT h e c h ν ν π ν ρ 3 3 8 c h B A nm nm ν π = kT h m n e N N / ν = 1 1 ) ( ) ( = = n m nm nm n m n nm nm N N B A N N N B A ν ρ rate prob rate prob Intensity rate probability τ 1

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