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**Emission and absorption of light; a shape of the emission band
**

β

hν

Ψ = a α +b β

α

General introduction to the problem We shall consider a quantum-mechanical system (QMS) with discrete energy levels Incident light will be treated classically (as a monochromatic plane wave) In a QMS with a discrete spectrum there are three types of transitions between energy levels Ψ2 Ψ2 Ψ2 hν W12 ind hν W21 ind hν A21 hν sp Ψ1 Ψ1 Ψ1 Induced absorption with probability W12ind Induced emission with probability W21ind Spontaneous emission with probability W21sp Probability = number of transitions per 1 second! [W]=s-1 .

polarization. . phase. which induced the transition (their energy. direction of propagation are all the same!) Spontaneous transitions can not be interpreted classically Lifetime = ∞ (if no external force is applied!) “Classical” world Lifetime is FINITE (EVEN if no external force is applied!) “Quantum” world The probabilities of induced transitions are proportional to the volume density of the E/M field energy per unit spectral interval ([ρv]=J∙m-3∙Hz-1) W12 = B12 ρ v ind W21 = B21ρ v ind where B and B are Einstein’s coefficients for induced absorption and emission.General properties of induced and spontaneous transitions The probability of induced transitions is not zero if the incident photon energy hv equals energy difference between two states: hv = E2 –E1 The photons emitted as the result of induced transitions are identical to the photons.

Relations between Einstein coefficients and spontaneous emission rate E2 n2 n1 E − E1 n1 and n2 are the numbers of particles in the states 1 and 2. g1 = exp − 2 g 2 g1 kT and g2 are the degrees of degeneracy of these states E1 Total number (per second) of the “2→1” transitions is the number of particles in the “2” state multiplied by the probability of the “2→1” transition for one particle: + A21 = n2 ( B21 ρ v + A21 ) For the “1→2” transitions we have: N12 = n1W12 ind = n1 B12 ρν N 21 = n2W21 = n2 W21 ind ( ) T3 Equilibrium condition implies N12 = ρv = A21 B21 B12 B21 N21. The spectral density of E/M field energy 1 g1 E − E1 exp 2 −1 g2 kT 2 1 T3> T2> T1 Einstein supposed that the induced and spontaneous transitions obey the black body radiation distribution (Planck’s law) hv = E .E (Bohr postulate!) T2 T1 8πν 2 ρv = 3 c hν hν exp −1 kT B12 g1 = B21g 2 8π ν 2 A21 = 3 hν B21 c Probabilities of stimulated emission and spontaneous emission are proportional! .

Relations between Einstein coefficients and spontaneous emission rate (contd. on the contrary. Spontaneous emission. .) 8πν 2 3 hν + ρ v W21 = B21 c W21 depends on: v3 (not significant for the radio waves. getting stimulated emission between these states is IMPOSSIBLE! 2 Total probability of emission (including spontaneous and induced transitions) A21 = 8π ν hν B21 3 c Equilibrium condition for emission and absorption transitions is compatible with N. is a pure quantum mechanical phenomenon without any explanation based on classical physical theories. Stimulated transitions are in a certain sense analogous to the forced oscillations (with a resonant condition) in classical mechanics. Bohr postulate. Intensive radiation can enhance probability of the radiative transitions! If spontaneous emission is not allowed between two states. but important in the optical region) volume spectral density of the E/M field energy ρv .

Heisenberg): ∆E ⋅ ∆t ≥ ⇒ ∆ω ≈ 1 1 . ∆ν ≈ ∆t 2π ⋅ ∆t Finite lifetime of an excited level results in broadening of the emission lines! . Uncertainty relations (W.Natural width of emission lines Though the resonance condition hv = E2-E1 should be fulfilled (implying the transition to occur at the precisely defined energy hv). the emission bands have non-zero width.

but I know exactly where I was… Werner Heisenberg (1901 – 1976) Nobel prize in physics. 1932 Do you know how fast were you going? ∆p ⋅ ∆x ≥ h .Heisenberg relation No. I don’t.

ω 1= ω 01 − 2 2 2 ω 01= E2 − E1 .Natural width of emission lines The shape and width of the spontaneous emission band can be easily obtained in the classical approximation using an equation of motion for the damped oscillations + γ x + ω012 x = 0 x γt 2 γ Its solution is: x( t ) = A exp − ⋅ exp( iω 1t ) .

) The time dependent function x(t) is associated with its corresponding frequency-dependent function obtained by means of Fourier transform of x(t). . γ ∞ + i ( ω 1− ω ) 1 A 2 Spectral distribution of amplitudes g (ω ) = 2 ∫∞x( t ) ⋅ exp( − iω t ) dt = 2π ⋅ 2π − (form-factor) ( ω 1− ω ) 2 + γ 2 * A2 ⋅ Intensity distribution is defined as I ( ω ) = g ( ω ) g ( ω ) = 2π 1 ( ω 1− ω ) + γ 2 2 2 Full width at half maximum (FWHM) γ I max 2 A2 = I (ω 1 ) = πγ2 1 γ I max = I ω 1± 2 2 Lorentzian profile FWHM = γ Intensity of spontaneous (and induced) emission is frequency-dependent. Decrease of the excited state lifetime (increase of “friction” from the classical point of view) leads to increase of FWHM.Natural width of emission lines (contd.

Natural width of emission lines (contd.) Dependence of the FWHM on γ γ = 10 I (ω ) = 1 (10 − ω ) 2 + γ 2 2 γ=5 γ=1 γ=0 .

then each atom emits radiation with the same spectral shape and FWHM. If the lifetime τ is about 10 ns. In this case such a broadening is identical for all atoms. the natural width of emission lines can be estimated as an inverse value of the excited state lifetime. . δν= δω/(2π) = 1/(2πτ) = 16 MHz.Natural width of emission lines (contd. or about 10-8 from the visible light frequency. If we have an ensemble consisting of identical atoms. It is impossible to ascribe a definite spectral component g(ω) with intensity I(ω) to a definite atom.) For real systems. Emission line broadening caused by the finite lifetime of an excited level is referred to as the homogeneous broadening.

700 m/s. u for gases is about 500v − v0 = 0. . The shape of the emission band is defined then by velocity distribution of molecules.Inhomogeneous broadening (Doppler effect) All molecules (atoms) of a gas are in the state of thermal motion.0023 %. the frequency shifts are different too.5∙1014 Hz (400 nm). It leads to an apparent shift of the emission frequency for those emitters moving to/from an observer: u ν = ν 0 1 ± c N λ0 Nλ hν 0 u hν 1 λ< λ0 ν > ν0 Numerical estimation: for blue light ν0 is about 7. Then increase of ν: v0 Since the velocities of all particles are different.

where q(v) is a form-factor.) q (ν )dν = p (u )du .Inhomogeneous broadening (Doppler effect.Maxwell speed distribution for the ideal gas exp − 2k T u 2 1 p (u ) = exp − . and p(u) is a velocity distribution m p (u ) = 2π k T 2k T u0 = m q (ν ) = c u0ν 0 1/ 2 mu 2 . contd.The most probable speed u0 u0 π Gaussian profile 1/ 2 c 2 ν −ν 2 1 0 exp − 2 u0 ν 0 π qmax c 1 = u0ν 0 π c 2 ν −ν 2 1 c 1 0 qmax = exp − 2 ν u0 0 2 u0ν 0 π u0 ln 2 c ν = ν 0 ±ν 0 u0 ln 2 c FWHM = 2ν 0 A rough estimation gives about 10-6 from the visible light frequency (about 100 times wider than the natural width) .

Comparison between Lorentzian and Gaussian profiles (with equal FWHM) Gaussian FWHM Lorentzian .

Relations between different units in spectroscopy 1 Wave number ν = . λ = 1000 nm. ν = 25000 cm-1.000124 eV cm× Frequency ν = 29. ν = 10000 cm-1.0259 eV or 208.9865 ∙ 10-23 J cm× ν ν Energy (in eV) E =0. measured in cm-1. Energy (in J) E = 1.4 cm-1 . λ λ = 400 nm.978 ∙ 109 Hz cm × ν Temperature 300 K corresponds to 0.

Summary Spontaneous and induced transitions in a quantum mechanical system were considered by introducing Einstein coefficients for these transitions. the Doppler broadening is about 100 times greater than the natural width of emission bands. Demtröder. The Lorentzian and Gaussian profiles for the emission lines were obtained and compared with each other. Laser Spectroscopy. Relations between basic spectroscopic units were considered. 1982 . For visible light. basic relations between these coefficients were established. Springer. Literature: W.

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