Absorption Spectrum and Color

780 nm 380 nm
= 1.6 eV = 3.3 eV 1
Absorption spectrum
defined as a degree of light absorption (absorbance) as a
function of the wavelength of light

the absorption of light is often due to loosely bound

electrons in bonds or  molecules orbitals

Resonance
Delocalized electrons are held more loosely than
locaized electrons and are able to move from one
bond or atom to another

2
Example: Yellow color
The solution containing a certain dye (yellow)
exhibit yellow because the molecules absorb
the violet light, which is complementary color
of yellow-green

Color & Complementary color

recognized
Wavelength-color relation of the light
400-435 nm violet
435-480 nm blue
500-560 nm green
580-595 nm yellow
absorption
610-750 nm red
3
 Visible light (l = 380 ̶ 780 nm)

Emitting light with a certain wavelength

Emitting light with a wide range of wavelengths

colored light
white light

Absorbing light of certain wavelengths

Absorbing light of whole wavelengths
Color & Complementary color

recognized

Vantablack
The worlds darkest material (absorbing
99.965% of radiation in the visible region)

‫مسجد نصیر الملک‬ absorption 2

When the light is absorbed, a molecule in a
ground state is promoted to an excited state.
This corresponds to that an electron in the
molecule is excited from its originally
occupying energy level to a higher level.
Therefore, transition energy of an electron
can be determined from the maximum
wavelength in the absorption spectrum.
Since, this energy reflects an electronic state of
the molecule and the molecular structure, it is
possible to estimate them by measuring
absorption spectra.
5
 Light absorption by a matter
Energy levels An electron excitation An electron can be promoted only
of a molecule when the photon energy matches
by light absorption.
the energy difference between two
unoccupied levels

levels.

ℎ𝑐
𝐸𝑖 = ℎ𝜈𝑖 =
𝜆𝑖
LUMO
Ei ; energy difference between the levels
h ; Planck constant
c ; speed of light
ni ; frequency of the light
li ; wavelength of the light

HOMO Absorption Spectrum

occupied levels

hn1+a
Absorbance

The photon energy hn1+a hn4 hn3 hn2 hn1

ground state does not match any of the Wavelength 3
energy differences.
Example 1: A colored solution was prepared by solving a
reagent into the ethanol solution. The reagent is a molecule
which has a one dimensional (ID)  conjugated structure. As
an ultraviolet/visible absorption spectrum of the colored
solution was measured, the absorption spectrum gave an
absorption maximum at 423 nm.
A) Calculate the energy difference (in ev) between the
HOMO and LUMO level

7
Answer:
Provided that blank constant (h)= 6.626 x 10-34 & Speed of
light (c)= 2.99 x 108

E = h x c / lmax =
lmax should be in meter . So,
to convert nm to meter divide it by 10 9
423 x 10 -9
E = (6.626 x 10-34 x 2.99 x 108 ) / 423 x 10 -9 = 4.969 x
10-19 J
to convert it to ev
E = (4.969 x 10-19 / 1.602 x 10-19) = 2.93 ev 8
 Absorption spectrum and electronic structure
visible light region Expected electronic
structure
LUMO+2
LUMO+1
LUMO

1.95 eV

1.77 eV

1.62 eV
3,3'−diethylthiatricarbocyanine iodide
765 nm
2 =1.62 eV HOMO
Absorbance

LUMO

1.62 eV
1.77 eV
1.95 eV
702 nm
1 =1.77 eV
HOMO
HOMO ̶ 1
636 nm HOMO ̶ 2
=1.95 eV
LUMO+1
0 LUMO
400 600 800

1.77 eV
1.95 eV

1.62 eV
Wavelength (nm)

The HOMO-LUMO gap energy HOMO

4 of 1.62 eV is assured. HOMO ̶ 1
 Purpose of the present experiment
A cyanine molecule with
[Experiment 1] an unknown HOMO-LUMO
gap energy. [Experiment 2]
(1) Measure absorption spectra
of the solution in which a LUMO (3) Build a model molecule
cyanine molecule is dissolved. by a commercial software
hn (Spartan Student Edition).
2
Absorbance

H 2N N H 2+
1 HOMO x

0
400 600 800
Wavelength (nm)

(4) Carry out molecular

orbital (MO) calculations to
(2) Determine the wavelength theoretically determine the
of the absorption maximum electronic structure and the
and estimate the HOMO- shape of the MOs.
(5) Compare the
LUMO gap energy. results and make
LUMO
a discussion
ℎ𝑐
𝐸HOMO−LUMO =
𝜆max
HOMO
5
 Cyanine pigment & 1D  conjugated system
one dimensional (1D)
 conjugated system

N +
N
x

+ N
N
Conjugated system: the system
x
f altering single and double
carbon bond
0.5+
N N 0.5+
x
Electron delocalization generally  electrons are delocalized across
lowers the energy of the molecule the entire chain between two N atoms.
6 and increases stability.
 Molecules with 1D  conjugated system
Mother nature produces many kinds of
molecules with 1D conjugated systems.
b-carotene

lutein

lycopene

Color and the length of the conjugated system

piperylene heptatriene LUMO 3.35-to-1.61 eV < 26 meV

> 3.35 eV

Colorless HOMO coloration metallic conductivity

colorless
(Do not absorb visible lights.)
Length of the 1D conjugated chain 7
 Gap energy vs. Length
LUMO 3.35-to-1.61 eV < 26 meV HOMO-LUMO
gap energy
> 3.35 eV ℎ2
∆𝐸 = (2𝑁 + 1)
HOMO coloration metallic conductivity integer 8𝑚𝑒 𝐿2
colorless
Length of
Length of the 1D conjugated chain the 1D chain

h ; Planck constant
me ; mass of an electron

HOMO−LUMO gap energy

(log−scale)
absorption spectrum
2 ∆𝐸 ∝ 𝐿−2
Absorbance

1 Length of the 1D conjugated system

0
400 600 800
Wavelength (nm)

8
Transmission spectrum & Absorption spectrum
reflection
mirror

IA I0 1.0
transmission spectrum
a cell with a solvent

Transmittance
half mirror

0.5
IA I
a cell with a solution T = I / I0
0.0
400 600 800

𝐼 2
A = −logT
transmittance 𝑇= Absorbance
𝐼0 absorption spectrum

absorbance 𝐴 = −log 𝑇
0
400 600 800
Wavelength (nm) 9
 Particle-in-a-box model
The behavior of the electrons in
the 1D  conjugated system can
be approximated by a particle-in-
V
a-box model.

The simplest "particle-in-a-box" model

A particle (an electron) is confined in a 1D potential well.
x
The particle is allowed to move only along an x axis. 0 L
Note; the axis is not necessarily straight.

The potential V is zero between x = 0 and L E 𝜓

and is infinitely high at 0 < x and x < L. E4 0

Schrödinger equation
𝜓
ℏ2 𝑑 2
− 𝜓 𝑥 = 𝐸𝜓 𝑥 , where 0 <x<L. 0
2𝑚𝑒 𝑑𝑥 2
E3

By solving the Schrödinger equation, you obtain both 𝜓 𝑥 and 𝐸:

𝜓
2 𝑛𝜋 𝑛2 ℎ 2
𝜓 𝑥 = sin 𝑥 , 𝐸𝑛 = (n = 1, 2, 3, ...) E2 0
𝐿 𝐿 8𝑚𝑒 𝐿2
𝜓
E1 0
x
10 0 L
HOMO-LUMO gap energy in a particle-in-a-box model

2N electron system

The HOMO and LUMO levels are the Nth and (N+1)th levels.
e.g.) 2N = 6 You can count the number of
 electrons if the chemical
(𝑁 + 1)2 ℎ2 formula is known.

LUMO n=N+1 𝐸𝑁+1 =

8𝑚𝑒 𝐿2 ℎ2
∆𝐸 = (2𝑁 + 1)
8𝑚𝑒 𝐿2
𝑁 2 ℎ2
HOMO n=N 𝐸𝑁 =
8𝑚𝑒 𝐿2
Determinable from the
absorption spectrum.
The length of the 1D
𝑛2 ℎ 2  conjugated chain
𝐸𝑛 =
8𝑚𝑒 𝐿2 can be estimated.

E is diminished with L.

11
 How many  electrons are there?
x = 0, 1, 2, 3

From the measurements.

chemical formula total  electrons ℎ2

∆𝐸 = (2𝑁 + 1)
electrons 2N N E L 8𝑚𝑒 𝐿2
x=0 (C19H19N2S2)+ 178 6 3
x=1 (C21H21N2S2)+ 192 8 4
x=2 (C23H23N2S2)+ 206 10 5
x=3 (C25H25N2S2)+ 220 12 6

12
For example ... Planck constant ; h = 6.626×10−34 Js
electron mass ; me = 9.11×10−31kg
ℎ2
∆𝐸 = (2𝑁 + 1) [J] = [kg m2 s-2]
8𝑚𝑒 𝐿2
1 eV = 1.602 ×10−18J
1/2
ℎ2
𝐿= 2𝑁 + 1
8𝑚𝑒 ∆𝐸 E = 765 nm = 1.62 eV

3,3'−diethylthiatricarbocyanine iodide
2

Absorbance
1

x=3
Number of  electrons ; 2N = 12 0
400 600 800
Wavelength (nm)

L = 1.73 nm
N N
C-C ; 0.154 nm
C=C; 0.147 nm L = 1.5 nm
C-N; 0.13-0.14 nm
Example 2:
b) If the previous ID conjugated system of this molecule is
composed of 8  electrons and can be approximately
approximated by a ID particle in a box model, estimate the
length of the conjugated system.

19
Example 2:

2N=8
4.696 x 10-19 = (8+1) x (6.626 x 10-34)2 / (8 x 9.109 x 10-31 L2)
L 2= 1.17 x 10-18
L= 1.08 x 10-9 m
L = 1.08 nm

20
 MO calculations using SPARTAN
Four steps to obtain the energy levels.
(1) Build model molecules.
(2) Conduct a MO calculation under the Hartree-Fock approximation.
(3) Display the calculated result and extract values you need (E).
(4) Measure the length between two N atoms (L).

Model molecules
H H H H
+ N +
N N N
H H

x=0
H H

x=L
x x
x = 0, 1, 2, 3 x = 0, 1, 2, 3

One further step to obtain the molecular orbital shapes

(5) Calculate 𝜓 2 .
lobe
The Born rule node
|𝜓|2

The probability density of finding the particle is

(n = 3)
proportional to 𝜓(𝑥) 2 . 0
13
x=0 x=L
 2N, E, and L of model molecules
Model molecules
H H
N +
N
H H
x
x = 0, 1, 2, 3 From the MO calculations.

chemical formula total  electrons

electrons 2N N E L L
x=0 (C3H7N2)+ 38 6 3
x=1 (C5H9N2)+ 52 8 4
x=2 (C7H11N2)+ 66 10 5
x=3 (C9H13N2)+ 80 12 6

From the equation;

The validity of the particle-in-a-box model ℎ2
∆𝐸 = (2𝑁 + 1)
can be estimated from the comparison of 8𝑚𝑒 𝐿2
these two L values
14
 Shape of  orbitals
x = 0 model molecule
There are several s orbitals aside from the  orbitals.
H H How to find the  orbitals?

+ x
N N
H H z
H H H y
H N C N H
C C
There are six  electrons. H H

There are five  orbitals;

three of them are doubly occupied, (1) The  orbitals are composed of 2px atomic orbitals.
(2) The 2px orbital has a node on the molecular plane.
and two are unoccupied.
(3) All  orbitals have a node on the plane.
(4) The shape of the MOs is symmetric with respect to
LUMO+4
the plane.
LUMO
HOMO
HOMO-1
HOMO-2

15