Absorption

• Optical spectral regions and respective range

Absorption in organic
molecules
 UV, Visible and IR
-. Energy
-. Wavelength
-. Visible color
Absorption
• Ultra-violet (UV) region

-. UV A: 390nm ~ 320 nm
-. UV B: 320nm ~ 290nm
-. UV C: 290nm ~ 200nm Earth surface: UV A » UV B » UV C
Absorption
• Visible region
The spectrum does not contain all
the colors that the human eyes
and brain can distinguish.

only from mixed wavelength

-. Pure color from single wavelength

vs Which one is correct ??

Absorption
• Absorption vs Transmittance
Absorption and transmittance are
conceptually opposite phenomena
Absorption
• Infra-red (IR) region

-. Far IR (FIR): 1mm ~ 25 μm

-. Middle IR (MIR): 25 μm ~ 2500nm
-. Near IR (NIR): 2500nm ~ 770nm

NIR
-. fiber optic telecommunication
-. night vision google

MIR
-. Heat tracking missile
Absorption
• Electronic transition

Excited state (higher energy)

Electronic transition

Absorption in organic molecules covers

Ground state (lower energy) UV, visible and NIR regions

Molecular orbital
σ-bond π-bond
-. two s orbitals -. two p orbitals
-. one s and one p orbitals
-. two p orbitals
Absorption
FYI: Atomic orbital

In quantum mechanics, an atomic orbital is a mathematical function that describes the

wave-like behavior of either one electron or a pair of electrons in an atom. This function can
be used to calculate the probability of finding any electron of an atom in any specific region
around the atom's nucleus.
Absorption
FYI: Molecular orbital energy diagram

• Molecular orbital diagrams are diagrams of

molecular orbital (MO) energy levels,
shown as short horizontal lines in the center,
flanked by constituent atomic orbital (AO)
energy levels for comparison, with the
energy levels increasing from the bottom to
the top. Lines, often dashed diagonal lines,
connect MO levels with their constituent
AO levels.

• Degenerate energy levels are commonly

shown side by side.
Absorption

One σ and one π bonds between two carbons

atomic orbital of carbon Molecular orbital of ethylene

σ*
π*
p p absorption
sp2 sp2 π
x3 σ x3

Ethylene: main absorption from π-π* transition

σ-σ* transition requires a much higher energy
Absorption
If molecule contains atoms having non-bonding orbital

formaldehyde

possible transition and related energy

σ-σ* > σ-π* > n-σ* > π-π* > n-π*

Absorption intensity
In general, π-π* transition shows higher
absorption intensity than n- π* transition, due to
symmetry matching issue (dipole-dipole transition)

π-π* transition: molar absorptivity ~ 10,000 cm-1

n-π* transition: molar absorptivity ~ 2000 cm-1
Absorption
HOMO & LUMO
HOMO: highest occupied molecular orbital
(electron-occupied)
LUMO: lowest unoccupied molecular orbital
(electron-unoccupied)
HOMO-LUMO: optical band-gap (Eg)

examples
LUMO
σ*
π*
Absorption
(band-gap) (none-bonding orbital)
π
σ
HOMO

Ethylene Formaldehyde
Absorption
Spin-multiplicity
-. Spin quantum number of electron (s) is 1/2 or -1/2
-. Total spin quantum number (S)

-. Spin-multiplicity, M = 2S + 1
M = 1, singlet
M =3, triplet
-. Ground state: singlet state (M = 1)
-. Excited state: singlet and triplet coexists
singlet excited state: no spin change
triplet excited state: spin change
(inter-system crossing)

-. Singlet-singlet transition
-. Singlet-triplet transition
Absorption
Conjugation (electron delocalization)
alternating saturated (single) and unsaturated (double, triple) bonds

Non-pair electron in nitrogen

provide p-orbital overlap

-. Electron delocalization
benzene
Absorption
-. Conjugation length vs absorption wavelength

Eg

As conjugation length increases, absorption

n wavelength red-shifts (lower energy)
14

-. Effective conjugation length

Determining practical absorption wavelength

thermodynamic effect
(entropy)
Absorption
• Transition probability
Beer-Lambert law

α : absorption of 1 molecule
A: absorbance
z : thickness
N: number of total molecule
ε : molar absorptivity
(molar absorption coefficient)
c : concentration
a: absorption coefficient for film

=− × × × = × × ( ′ )

= = × × = × ( )
Absorption
Oscillation theory (absorption probability)

Light: electro-magnetic wave

Electric field: electron transfer

-. Unpolarized and linear polarized lights

Electric field direction Existing electron oscillates according
to electric field direction

unpolarized light polarized light

(sun light)
Absorption
-. Circular polarized light

Quarter-wave retardation
Retardation direction
Absorption

Retardation direction
X & Y components of linear polarized light
Absorption
-. Anti-reflection mechanism of circular polarizer

Light propagation Light propagation

reflection
Left-handed circularly polarized light Right-handed circularly polarized light

Linear polarizer Polarization

direction

Retardation film

Pol filter in OLED

Linear polarized light
(anti-reflection)
Absorption
-. Random orientation vs electron oscillation

Ground and excited states have different

dipole moment direction

ground state excited state

Dipole in molecules

Net dipole direction is the direction of

electron transition within molecule

water
Absorption
Transient dipole
- Dipole direction change between ground and
excited states
- Absorption happens only when the transient
dipole matches with light oscillation direction

geometry

examples

Absorption (excitation) vs polarized light

Absorption
-. Oscillator strength (f)
Quantitative ratio between transition and bound electron of ground state
Transition moment: transient dipole resulting from displacement
(transition between an initial state and a final state)
Examples of molar absorption coefficients

High transition moment

≈ high oscillator strength ≈ high absorption coefficient ≈ intense absorption
e.g.) π-π* transition ~ in plane of transition moment

Low transition moment (e.g. n-π*)

≈ low oscillator strength ≈ low absorption coefficient ≈ weak absorption
Absorption
-. Conjugation direction vs electron oscillation
absorption intensity of polarized light

Aligned conjugated polymer direction

Conjugation direction is an electron
Conjugation direction
oscillation pathway

Linear polarizer

Iodine growth

stretched cellulose
Absorption
• Selection rule
Spin-forbidden transition
Transition between states of
different multiplicities are forbidden

singlet-singlet or triplet-triplet transition: allowed

singlet-triplet or triplet-singlet transition: forbidden

Exception: spin-orbit coupling (inter-system crossing)

Symmetry-forbidden transition
Transition can be forbidden for symmetry reason

dipole-dipole transition
If initial-dipole and final-dipole are overlapped: allowed
If initial-dipole and final-dipole are non-overlapped: forbidden
Absorption
• Frank-Condon principle
Electronic transition is most likely to occur without change in the positions of nuclei
in the molecular entity (vertical transition)

electronic transition: 10-15 s

rotational transition: 10-12 s
vibrational transition: 10-13 s
vibration periods: 10-11 s

Absorption broadening
Homogeneous broadening
 Vibrational sublevels

Inhomogeneous broadening
 Environmental effect (solvation)
Absorption
• Multiphoton absorption
Single photon absorption
 same energy with the difference between the ground state and the excited state

Multi-photon absorption
 Absorption happens via short-lived virtual states only when the lifetime of
excitation light is much shorter (10-18 s) than electronic transition (10-15 s)

Example: two photon-absorption

Multi-photon absorption implies that light source having

lower energy than optical band-gap can be absorbed in
molecules