The application of quantum

mechanics: Spectroscopy
Atkins, Chapter 17

Transitions between Bohr frequency Exception:

defined energy states condition Raman scattering

wavelength

wavenumber
[cm-1]

Nils Walter: Chem 260

 The electromagnetic spectrum

Oscillating current
in metal wire

Klystron Deuterium
discharge
Quartz heated by
mercury arc
Nernst filament Tungsten-iodine lamp
(black body)
Nils Walter: Chem 260
 A spectrophotometer

Dispersing element
Nils Walter: Chem 260
 Resolution limits: 1. Line broadening
through the Doppler effect
Radiation source receding from observer:

speed
Radiation source approaching observer:

Overall effect on the linewidth:

temperature

mass
→ particularly in gases Nils Walter: Chem 260
 Resolution limits:
2. Collision broadening
Particle collision
⇓
deformation of involved particles
⇓
changes in electronic, vibrational, rotational states
⇓
transitions less well defined
⇓
line broadening

→ particularly in liquids or
gases under high pressure
Nils Walter: Chem 260
 Resolution limits - the bottom line:
3. Lifetime broadening
Solving the time-dependent Schrödinger
equation reveals Heisenberg’s
uncertainty principle: ⇒
practical
Lifetime of excited state;
determined by
collisional deactivation
and spontaneous emission
Gases @ low pressure unchangeable
enable high-resolution
⇒ natural linewidth
spectroscopy
Nils Walter: Chem 260
 The intensity of spectral lines
depends on:
• the transition probability
between the two states
(selection rules)
• population of states
Boltzmann
constant

• path length of sample

(Lambert-Beer law)
extinction
coefficient Nils Walter: Chem 260