Lecture 2

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

= a +b

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
2 2 2

h
W12
ind

h
W21
ind

h
A21 h
sp

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

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, which induced the transition (their energy, phase, polarization, 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 ([v]=Jm-3Hz-1)

W12 = B12 v

ind

W21 = B21 v

ind

where B and B are Einsteins coefficients for induced absorption and emission.

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 21 transitions is the number of particles in the 2 state multiplied by the probability of the 21 transition for one particle:

+ A21 = n2 ( B21 v + A21 ) For the 12 transitions we have: N12 = n1W12 ind = n1 B12 N 21 = n2W21 = n2 W21
ind

T3

Equilibrium condition implies N12 =

v =

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 (Plancks law) hv = E - E (Bohr postulate!)

T2 T1

8 2 v = 3 c

h h exp 1 kT

B12 g1 = B21g 2
8 2 A21 = 3 h B21 c

Probabilities of stimulated emission and spontaneous emission are proportional!

Relations between Einstein coefficients and spontaneous emission rate (contd.)

8 2 3 h + v W21 = B21 c
W21 depends on: v3 (not significant for the radio waves, but important in the optical region) volume spectral density of the E/M field energy v . Intensive radiation can enhance probability of the radiative transitions! If spontaneous emission is not allowed between two states, getting stimulated emission between these states is IMPOSSIBLE! 2
Total probability of emission (including spontaneous and induced transitions)

A21 =

8 h B21 3 c

Equilibrium condition for emission and absorption transitions is compatible with N. Bohr postulate. Stimulated transitions are in a certain sense analogous to the forced oscillations (with a resonant condition) in classical mechanics. Spontaneous emission, on the contrary, is a pure quantum mechanical phenomenon without any explanation based on classical physical theories.

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.
Uncertainty relations (W. Heisenberg):
E t 1 1 , t 2 t

Finite lifetime of an excited level results in broadening of the emission lines!

Heisenberg relation

No, I dont, 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

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

+ x + 012 x = 0 x
t 2 Its solution is: x( t ) = A exp exp( i 1t ) , 1= 01 2 2
2

01=

E2 E1

Natural width of emission lines (contd.)

The time dependent function x(t) is associated with its corresponding frequency-dependent function obtained by means of Fourier transform of x(t). + i ( 1 ) 1 A 2 Spectral distribution of amplitudes g ( ) = 2 x( t ) exp( i t ) dt = 2 2 (form-factor) ( 1 ) 2 +
2
*

A2 Intensity distribution is defined as I ( ) = g ( ) g ( ) = 2

( 1 ) + 2
2

Full width at half maximum (FWHM)

I max 2 A2 = I ( 1 ) = 2 1 I max = I 1 2 2

Lorentzian profile

FWHM =

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.)

Dependence of the FWHM on
= 10

I ( ) =

(10 ) 2 + 2

=5

=1

=0

Natural width of emission lines (contd.)

For real systems, the natural width of emission lines can be estimated as an inverse value of the excited state lifetime. If the lifetime is about 10 ns, = /(2) = 1/(2) = 16 MHz, or about 10-8 from the visible light frequency.

Emission line broadening caused by the finite lifetime of an excited level is referred to as the homogeneous broadening. If we have an ensemble consisting of identical atoms, then each atom emits radiation with the same spectral shape and FWHM. It is impossible to ascribe a definite spectral component g() with intensity I() to a definite atom. In this case such a broadening is identical for all atoms.

Inhomogeneous broadening (Doppler effect)

All molecules (atoms) of a gas are in the state of thermal motion. It leads to an apparent shift of the emission frequency for those emitters moving to/from an observer: u
= 0 1 c
N 0 N

h 0

h 1

< 0 > 0

Numerical estimation: for blue light 0 is about 7.51014 Hz (400 nm); u for gases is about 500v v0 = 0.0023 %. 700 m/s. Then increase of :
v0

Since the velocities of all particles are different, the frequency shifts are different too. The shape of the emission band is defined then by velocity distribution of molecules.

Inhomogeneous broadening (Doppler effect; contd.)

q ( )d = p (u )du , where q(v) is a form-factor, and p(u) is a velocity distribution m p (u ) = 2 k T 2k T u0 = m q ( ) = c u0 0
1/ 2

mu 2 - Maxwell speed distribution for the ideal gas exp 2k T u 2 1 p (u ) = exp - The most probable speed u0 u0
Gaussian profile

1/ 2

c 2 2 1 0 exp 2 u0 0

qmax

c 1 = u0 0

c 2 2 1 c 1 0 qmax = exp 2 u0 0 2 u0 0 u0 ln 2 c

= 0 0

u0 ln 2 c

FWHM = 2 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 = ; measured in cm-1. = 400 nm; = 25000 cm-1; = 1000 nm; = 10000 cm-1;
Energy (in J) E = 1.9865 10-23 J cm

Energy (in eV) E =0.000124 eV cm

Frequency = 29.978 109 Hz cm Temperature 300 K corresponds to 0.0259 eV or 208.4 cm-1

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

Literature: W. Demtrder, Laser Spectroscopy, Springer, 1982

A small exercise
Radiation type Gamma rays X-Rays UV Visible IR Microwave TV Radio Wave-length (m) <10-11 10-11 10-9 10-9 10-7 10-7 10-6 10-6 10-4 10-4 10-1 10-1 101 >101 Wave-length Frequency (nm) (Hz) Energy (cm-1) Energy (J) Energy (eV)

NK A TH

!! U O Y