Interaction with matter Energy levels Degrees of Freedom

Spectroscopy
Rotational Spectroscopy Vibrational Spectroscopy
microwave infrared

Electronic Transitions

Absorption Spectroscopy Emission Spectroscopy

 Introduction to Matters

Rotational Spectroscopy

Vibrational Spectroscopy

Absorption and emission Spectroscopy

Atkins, Physical Chemistry, 9th edition, 2009
Banwell & McCash, Fundamentals of Molecular Spectroscopy, 4th edition, 1996
Lakowicz, “Principles of Fluorescence Spectroscopy”, Springer Publishers, 3rd Edition, 2011
Moog, Spencer and farrell, Physical Chemistry: A Guided Inquiry: Atoms, Molecules,
and Spectroscopy, 2003
• The sun produces a full spectrum of electromagnetic
radiation

http://csep10.phys.utk.edu/astr162/lect/light/spectrum.html

http://kr.blog.yahoo.com/bmw26z/2188
Components of Electro Magnetic
Radiation

v
 Two Components of EM
Radiation
• Electrical field (E): varies in magnitude in a direction
perpendicular to the direction of propagation
• Magnetic field (M): at right angle to the electrical
field, is propagated in phase with the electrical field
• Wavelength (l), distance from one wave crest to another
• Frequency (n), No. of crests passing a fixed point/ given time
• Amplitude, height of each peak (watts/sq. meter

• The speed of EM energy “c” 300,000km/second,

c = nl where l and n are inversely related
 Interaction of radiation with matter

Wavelength
• If there are no available quantized energy levels matching the quantum
energy of the incident radiation, then the material will be transparent to that
radiation
 Fate of molecule?

• Non-radiative transition: M* + M  M + M + heat

• Spontaneous emission: M*  M + hn (very fast for large
DE)
• Stimulated emission (opposite to stimulated absorption)

These factors contribute to linewidth & to lifetime of excited

state.
 Molecular Motion and Spectroscopy

Study of Interaction of Matter and Light (Photon)

• Molecular Spectroscopy
 Information about molecules such as geometry and energy
levels are obtained by the interaction of molecules and photons

• Molecular motions: Translation, Rotation, Vibration

 determines the energy levels for the absorption or emission of
photons
Electronic, Vibrational, and Rotational Energy Levels of a
Diatomic Molecule

Exercise: Indicate the

molecular state in which it is
electronically in the ground
state, vibrationally in the first
excited state, and rotationally
in the ground state.
 ROTATIONAL
SPECTROSCOPY
 Microwave interactions

• Quantum energy of microwave photons (0.00001-0.001 eV) matches the ranges

of energies separating quantum states of molecular rotations and torsion

• Note that rotational motion of molecules is quantized, like electronic and

vibrational transitions associated absorption/emission lines

• Absorption of microwave radiation causes heating due to increased molecular

rotational activity
Molecular rotations
 Types of Rigid Rotors
• A schematic illustration of the
classification of rigid rotors.
 RIGID ROTOR
Figure 40-16 goes here.

A diatomic molecule can rotate

around a vertical axis. The
rotational energy is quantized.
 THE RIGID ROTOR
A diatomic molecule may be thought of as two atoms held
together with a massless, rigid rod (rigid rotator model).
• Consider a diatomic molecule with different atoms of mass
m1 and m2, whose distance from the center of mass are r1 and
r2 respectively

 r1 | r2 
o o
m1 m2
• The moment of inertia of the system about the center of
mass is:

I  m1r12  m2 r22
 The Definition of Moment of
Inertia
• In this molecule
– three identical atoms
attached to the B atom
– three different but mutually
identical atoms attached to
the C atom.
• Centre of mass lies on the
C3 axis
• Perpendicular distances
are measured from the
axis passing through the B
and C atoms.
 Rotational levels
• The classical expression for energy of rotation is :In the
harmonic oscillator model, the energy was all potential
energy. In the rigid rotor, it’s all kinetic energy:
• I 2 L2
Er   where L angular momentum
2 2I
2
 h 
L    J ( J  1)
2

 2 

• where J is the rotational quantum number

2
1  h 
E(J )    J ( J  1)  h c Bn J ( J  1)
2 I  2 
h
Bn  the rotational constant
8 c I
2
 Quantization of Rotational Energy

V=0
cyclic boundary condition: Ψ(2π + θ) = Ψ(θ)
By solving Schrodinger equation for rotational motion

the rotational energy levels are

Rotational energy levels in wavenumber (cm-1)

h
(B  )
8 cI
2
Spacing between adjacent rotational levels j and j-1)
 The Gross Selection Rule for
Rotations
• A rotating polar
molecule looks like
an oscillating dipole
which can stir the
electromagnetic field
into oscillation.
• Classical origin of
the gross selection
rule for rotational
transitions.
Rotational Spectroscopy

(1) Bohr postulate

D  hn  hc / l
(2) Selection Rule
Dj  1
Dj  1 (absorption)
Dj  1 (emission)
Vibrational Motion: Molecular Calisthenics
Harmonic oscillator

F  k (r  re )

1
 vib   2 1014 s
n
A molecule vibrates ~50 times
during a molecular day (one rotation)
Quantization of Vibrational Energy
By solving Schrodinger equation for vibrational motion,
Vibrational energy level

where is a vibrational quantum number

Zero point energy

Spacing between adjacent vibrational sates

 ROTATIONAL SPECTRUM

Selection Rule: Apart from

Specific rule- DJ 1, Gross
rule- the molecule should have
a permanent electric dipole
moment, m . Thus, homonuclear
diatomic molecules do not have
a pure rotational spectrum.
Heteronuclear diatomic
molecules do have rotational
spectra

Dj  1
Dj  1 (absorption)
Dj  1 (emission)
Appearance of rotational spectrum We can calculate
the energy corresponding to rotational transitions

D E=EJ’ –EJ for DJ  J final  J initial  1

Or generally:
J  J + 1 ν = B(J+1)(J+2) - BJ(J+1)

ν= 2B(J+1) cm-1

Microwave absorption lines should appear at

J = 0  J = 1 : = 2B - 0 = 2B cm-1
J = 1  J = 2 : = 4B cm-1

Note that the selection rule is DJ = 1, where +

applies to absorption and - to emission.
Relative Intensities of rotation spectral
lines
Now we understand the locations (positions)
of lines in the microwave spectrum, we can
see which lines are strongest.

J  BJ(J+1)

J=0  0

Intensity depends upon two factors:

Intensity depends upon two factors:
1.Greater initial state population gives stronger spectral
lines.This population depends upon temperature, T.

NJ  E   hcν 
 exp  J   exp  
N0  kT   kT 

k = Boltzmann’s constant, 1.380658 x 10-23 J

K-1
(k = R/N)
NJ  1.52034 ν  hc
 e    1.52034 cmK
No  T  k

We conclude that the population is smaller for

higher J states.
2. Intensity also depends on degeneracy of initial
state.

(degeneracy = existence of 2 or more energy states having exactly

the same energy)
Each level J is (2J+1) degenerate
 population is greater for higher J states.

To summarize: Total relative population at energy

EJ  (2J+1) exp (-EJ / kT) & maximum population
occurs at nearest integral J value to :

Look at the values of NJ/N0 in the figure, .

 Pop  (2J + 1) e ( -BJ(J + 1)hc/kT)

max.
pop.
B = 10cm-1
0 J
Plot of population of rotational energy levels
versus value of J.
 MCWE or Rotational Spectroscopy
Classification of molecules

• Based on moments of inertia, I=mr2

– IA  IB  IC very complex eg H2O
– IA = IB = IC no MCWE spectrum
eg CH4
– IA  IB = IC complicated eg NH3
– IA = 0, IB = IC linear molecules eg NaCl
 
J J 1 2

EJ  with J  0,1,2, also M J  0,1,  J

2I
Vibrational Spectroscopy
 Vibrational Spectra
Molecules are not Static
Vibration of bonds occurs in the liquid, solid and gaseous phase
Vibrating  Energy  Frequency (and the appropriate frequencies
for molecular vibrations are in the Infrared region of the
electromagnetic spectrum
Vibrations form therefore, a fundamental basis for spectroscopy in
chemistry--the bonds are what makes the chemistry work in structure
and function
For Organic Chemistry the most important uses of these vibrations is
for analysis of:
•functional groups
•structural identity, “fingerprinting”
What Kind of vibrations are These?
Bonds can…….
These can number into the
hundreds.
Bend Some are symmetrical, some
antisymmetrical and many are
coupled across the molecule
Can be calculated. One easy
Stretch approximation is:

k k is the “force constant”, like the

n = 5.3 ´ 10 -12
Hookes Law restoring force for a
m spring. Known and tabulated for
Wag different vibrations
m1m2
(rock) m= The “reduced mass” where m1, m2
m1 + m2 are the masses on either side of
vibration
 The Fundamentals
These oscillating electric
dipoles match in frequency
antisymmetric symmetric the incoming e-field
oscillations of IR light.
R R
H H All the simple possibilities.
stretching For n atoms in a molecule;
R H R H
– Linear: 3n – 5 modes
– Non-linear: 3n – 6
R R modes
H H in-plane – Example for a
R H bending methylene,given n=3
R H
scissoring rocking
While useful, this
R R oversimplifies, since
H H
out-of-plane molecular orbital picture
R H requires that atoms can’t
R H bending vibrate without affecting
wagging twisting the rest of the molecule.
 A Functional Group Chart
4000 3600 3200 2800 2400 2000 1600 1200 800 group
O-H str

NH str
COO-H
=C-H str
Csp3-H
C-H
-(C=O)-H

CN
CC
C=O
-C=N
-C=C
phenyl
C-O
C-N
F Cl C-X
Br
 Regions of Frequencies
Spectral Region Frequency(Hz) Wavenumber(cm-1) Wavelength (l,mm)
Near -to 3.8 x 1014 to 1.2 12800 to 4000 0.78 to 2.5
visible- IR x 1014
(NIR)
Combination
bands
Mid Infrared 1.2 x 1014 to 6.0 4000 to 200 2.5 to 50
Fundmental x 1012
bands for
organic
molecules
Far IR 6.0 x 1012 to 3.0 200 to 10 50 to 1000
Inorganics x 1011
organometallics
 Looking at a Spectrum
Divide the spectrum in to two regions:
4000 cm-1 1600 cm-1 most of the stretching bands,
specific functional groups
(specific atom pairs). This is the
“functional group” region.
1600 cm-1  400 cm-1 Many band of mixed origin. Some
prominent bands are reliable. This
is the “fingerprint” region. Use
for comparison with literature
spectra.

Wavenumber is cm-1=104/l(m)
 What kinds of Bonds Absorb in
which Regions?
Bending is easier than stretching-- happens at lower energy
(lower wavenumber)
Bond Order is reflected in ordering-- triple>double>single (energy)
with single bonds easier than double
easier than triple The k in the frequency
equation is in mDyne/Å of
Heavier atoms move slower than displacement
lighter ones
Single bond str 3-6 mD/Å
Double bond str. 10-12 mD/Å
Triple Bond 15-18 mD/Å
 Effects of conjugation
Lowers to
1715 cm-1

Raises to
1770 cm-1
Similar, to
1715 cm-1

:
Weakens DB
Strengthens DB
character
character (inductive
over resonance)
 Degrees of Freedom:
Translation, Rotation, and Vibration
Consider a single Ar atom moving in 3-D space:

- Moving motion is referred to as Translation

- To analyze the translation of an Ar, we need to know
position (x, y, z) and momentum (px, py, pz)
Where it is Where it is headed

- Each coordinate-momentum pair [for example, (x,px)] is

referred to as a Degree of Freedom (DF)

- An Ar atom moving through 3-D space has three DFs

N argon atoms possesses 3N DFs:

All translational DFs
 Center of Mass (Balanced
Point)
- A point mass that can represent the
molecule
- Motion of the center of mass requires 3 DFs
to describe it
- In general, regardless of its size or
complexity, a molecule has 3 translational
DFs
- Thus, (3N – 3) DFs for the internal motions
of rotation and vibration
Rotational and vibrational
DFs
N atomic N atomic
Linear Non-Linear
Molecule Molecule

Rotation 2 DFs 3 DFs

Vibration 3N – 5 3N - 6
 Vibrational Spectroscopy
Vibrational selection rule

D  1
D  1 (absorption)
D  1 (emission)
 The Vibrations of CO2.
• The stretching modes are not
independent, and if one CO
group is excited the other begins
to vibrate.
• The symmetric and
antisymmetric stretches are
independent, and one can be
excited without affecting the
other: they are normal modes.
• The two perpendicular bending
motions are also normal modes.
 The Normal Modes of Water
• The three normal
modes of H2O. The
mode v2 is
predominantly
bending, and occurs
at lower
wavenumber than
the other two.
Absorption and Emission Spectroscopy
 Electronic Transitions in Molecules

Molecular Orbital (MO) Theory

for C2H4 molecule,

UV or Visible
spectral region
Fate of Excited Electronic States

Department of Chemistry, KAIST

 Introduction to Absorption
Reflection and Scattering Losses
 LAMBERT-BEER LAW Power of
radiation after
passing through
the solvent
Psolution P
T   Power of radiation
Psolvent P0 after passing
through the sample
 P solution
A   log T   log  
 P0 
A  abc  kc
a  absorptivity
b  pathlength
c  concentration
 Beer’s law and mixtures
• Each analyte present in the solution absorbs light!
• The magnitude of the absorption depends on its 
• A total = A1+A2+…+An
• A total = 1bc1+2bc2+…+nbcn
• If 1 = 2 = n then simultaneous determination is
impossible
• Need nl’s where ’s are different to solve the mixture
 Molecular Transitions
for UV-Visible Absorptions
• What electrons can we use for these
transitions?
Spectral nomenclature of shifts
 Introduction to Emission
• Luminescence: emission of photons from
electronically excited states of atoms,
molecules, and ions.
• Fluorescence: Average lifetime from <10—10
to 10—7 sec from singlet states.
• Phosphorescence: Average lifetime from 10—5
to >10+3 sec from triplet excited states.
 Importance of Emission
Spectroscopy
• Sensitivity to local electrical environment
– polarity, hydrophobicity
• Track (bio-)chemical reactions
• Measure local friction (microviscosity)
• Track solvation dynamics
• Measure distances using molecular rulers:
fluorescence resonance energy transfer (FRET)
 Photophysics: Jablonski Diagram

Kasha’s rule, Internal Conversion, Intersystem crossing, fluorescence, phosphorescence

 Principles
• Interaction of photons with molecules
results in promotion of valence electrons
from ground state orbitals to high energy
levels.
• The molecules are said to be in excited
state.
• Molecules in excited state do not remain
there long but spontaneously relax to more
stable ground state.
• The relaxation process is brought about by
collisional energy transfer to solvent or
other molecules in the solution.
• Some excited molecules however return to
the ground state by emitting the excess
energy as light.
• This process is called fluorescence.
Light Amplification by Stimulated Emission of Radiation
 In a laser….

Three key elements in a laser

•Pumping process prepares amplifying medium in suitable state

•Optical power increases on each pass through amplifying medium
•If gain exceeds loss, device will oscillate, generating a coherentoutput