BASIC THEORY OF SPECTROSCOPY

Spectroscopy and electromagnetic radiation

Spectroscopy: involves the investigation of the

interaction of electromagnetic radiation with
matter and explanation of the spectral pattern.

Spectra: show how the interaction between

electromagnetic radiation and the matter varies
with the frequency of this electromagnetic
radiation.
Spectroscopy :
Study of absorption and/or emission of electromagnetic
radiation by atoms and molecules

Tells us about internal structure of atoms and molecules

• electronic energy levels
• molecular vibration : stretching and bending of bonds
• rotational energy level
Uses :
• determination of molecular structure
• identification of unknown molecules
• detection of known molecules
• measurement of concentration
Electromagnetic Radiation: consists of
orthogonal oscillating electric (E) and
magnetic (H) fields propagating through
space with velocity ( C )
C = 2.998 x 108 m/s
= 2.998 x 1010 cm/s ( in vacuum).

E
C
H
 420 470 530 580 620 700 nm

12800 3333 333 33 cm-1

NIR Mid IR Far IR
Visible

Spectral Regions

.. .UV Micro-
γ-Ray . X-Ray . .
IR
wave
ESR NMR
1 pm 100 pm 10 nm 1 μm 100 μm 1 cm 100 cm 10 m λ
Energy Level in Atoms :
• Electron in atoms exist in discrete energy level
- electronic energy level or electronic states
• Electronic energy is quantised
- first evidence from study of atomic spectra
- exited atoms (e.g in flame or electrical discharge)
emit light of particular wavelengths
- e.g emission spectrum of hydrogen atom
- Light emited when atoms loses electronic energy
- Atoms can lose electronic energy only in discrete
amount
- Therefore can exist only in series of discrete energy
levels
• e.g electronic energy level of hydrogen atom :
- electrronic energy depends on principal quantum number, n
Energy Levels in Molecules :
• Electronic energy :
- electron in discrete energy levels, as in atoms
• Vibrational energy :
- stretching and bending of bonds
- quantised
- vibrational energy levels
• Rotational energy :
- molecule spinning in space
- quantised
- rotational energy levels
 Etotal = Eel + Evib + Erot

• For each electronic level, there are several vibrational level

• For each vibrational level, there are several rotational level

Electronic Vibrational Rotational

Energy Level in molecules

Example: HCl vibration is observed at 2885 cm-1,express the vibrational energy

in Joul, Kilojoul/mole and meter.
 Molecule-light interaction
• Molecule: positively charged nuclei + negatively charged
electrons held together by Coulomb interaction
• Light interacts with charged particles  interaction is specific
to the nuclear and electronic “configuration” of the molecule
• Different types of motions in the molecule interact with light
differently
• Depending of frequency light interacts with different
“molecular degree of freedom”
TRANSITIONS
• When molecules absorbs or emits a photon its internal energy changes
• change from one energy level to another is called a transition
• Absorbtion of photon causes an upward transition to a higher energy
level (exitation)
• Emission of photon causes an downward transition to a lower energy
level

Energy of photon = difference in

energy between upper and lower
energy level

Ephoton = h = Eupper - Elower

• Electronic transition :
- transition from one electronic energy level to another
- difference in energy between electronic levels of same magnitude as
energy of photon of ultraviolet or visible light
- electronic transition occur in the UV and Vis region of electromagnetic
spectrum
• Vibrational transition :
- transition between vibrational energy levels
- difference in energy between vibrational levels much less then between
electronic levels
- difference in energy of same magnitude as photon of infrared radiation
- vibrational transitions occur in the infrared region
• Rotational transition :
- transition between rotational energy levels
- difference in energy between rotational levels less then
between vibrational levels
- difference in energy of same magnitude as photon of
microwave radiation
- rotational transitions occur in the microwave region
Frequencies in molecular spectroscopy

molecule spinning in space

 THE ELECTROMAGNETIC SPECTRUM
high Frequency (n) low
high Energy low

X-RAY ULTRAVIOLET INFRARED MICRO- RADIO FREQUENCY

WAVE

Nuclear
Vibrational magnetic
Ultraviolet Visible infrared
resonance
2.5 mm 15 mm 1m 5m
200 nm 400 nm 800 nm
BLUE RED

short Wavelength (l) long

 Types of Energy Transitions in Each Region
of the Electromagnetic Spectrum

REGION ENERGY TRANSITIONS

X-ray Bond-breaking
UV/Visible Electronic
Infrared Vibrational
Microwave Rotational
Radio Frequency Nuclear and
(NMR) Electronic Spin
 Rotational spectroscopy
• Microwave frequencies
• Absorption of photon causes transition to a rotational level of
higher energy
• Radiation energy is absorbed into the rotational energy of the molecule
 Vibrational spectroscopy
• Infrared frequencies
• Absorption of photons causes transitions to the vibrational
levels of higher energy
• Radiation energy is absorbed into the vibrational energy of the molecule

H2O
 UV/Visible spectroscopy
• “Soft” ultraviolet and visible frequencies
• Absorption of photons cause excitations of valence electrons
into unoccupied (but bound) states
 Photoelectron spectroscopy
• Ultraviolet – extreme ultraviolet frequencies
• Absorption of photons cause excitation of valence electrons
into the unbound states (ionization)
 X-ray absorption
• “Soft” x-ray frequencies
• Absorption of photons causes excitations of the corer
electrons into the bound unoccupied and unbound states