Chapter 17a

Fundamentals of
spectroscopy
1

Properties of Light

Types of Light – The Electromagnetic Spectrum

1
 Fundamentals of Spectrophotometry
17.4 Absorption of Light
Colors of Visible Light
 Many Types of Chemicals Absorb Various Forms of Light

 The Color of Light Absorbed and Observed passing through the Compound are
Complimentary

Absorption of light
17.4 Beer’s Law in chemical analysis

The relative amount of a certain wavelength of light absorbed (A) that passes
through a sample is dependent on:
- distance the light must pass through the sample (cell path length - b)
- amount of absorbing chemicals in the sample (analyte concentration – c)
- ability of the sample to absorb light (molar absorptivity - )

 Beer’s Law
A = bC
A = log(P0/P) = -logT
 Applies to monochromatic radiation
 Works very well in dilute solutions.
Increasing
[Fe2+]

4
Absorbance is directly proportional to concentration of Fe+2

2
 Beer’s Law
Absorbance is useful since it is directly related to the analyte concentration, cell
pathlength and molar absorptivity.
This relationship is known as Beer’s Law

The relative amount of light making it through the sample (P/Po) is known as the
transmittance (T) P
T
Po

P 
A   log    log(T )   log(%T / 100)
 Po 
A = bC
A = log(P0/P) = -logT
where: A = absorbance (no units)
 = molar absorptivity (L/mole-cm)
b = cell pathlength (cm)
c = concentration of analyte (mol/L)
Beer’s Law allows compounds
to be quantified by their ability
to absorb light, Relates directly P
to concentration (c)

Chapter 18 6

3
 16.4 What Happens When a Molecule Absorbs Light?

Molecule Promoted to a
More Energetic Excited
State
Absorption of UV-vis light results in an
electron promoted to a higher energy
molecular orbital

s  s*
transition in vacuum UV

n  s*
saturated compounds with non-bonding
electrons

n  p*, p  p*
requires unsaturated functional groups
(eq. double bonds)
most commonly used, energy good range for
UV/Vis

17.6 Absorption of light- Formaldehyde

 Consider formaldehyde: In its ground 120 pm

H
state, S0, the molecule is planar, with a
double bond between carbon and oxygen. O C 116.5o
From the electron dot description of
formaldehyde, we expect two pairs of H
nonbonding electrons to be localized on 110 pm
the oxygen atom. The double bond
consists of a sigma bond between carbon
and oxygen and a pi bond made from the
2py (out-of-plane) atomic orbitals of Excitation
carbon and oxygen.

By excitation, H
Formaldehyde becomes of pyramidal
structure in both the S1 and T1 excited 31o C 119o
states.
O
Promotion of a nonbonding electron to an H
antibonding C―O orbital lengthens the
C―O bond and changes the molecular 109 pm
geometry.
132 pm
Chapter 18 8

4
Electronic states of formaldehyde
In the molecular orbital (MO) diagram for
formaldehyde, one of the nonbonding AOs
of oxygen is mixed with the three sigma
bonding orbitals. These four orbitals, labeled
σ1 through σ4, are each occupied by a pair
of electrons with opposite spin (+ and -).

At higher energy is an occupied pi bonding

orbital (π), made of the py AOs of C and O.

The highest energy occupied MO (HOMO)

is nonbonding orbital (n), composed
principally of the 2px AOs from O.

The lowest energy unoccupied MO

(LUMO) is the pi antibonding
orbital (π*).

Electrons in this orbital produce repulsion,

rather than attraction, between the C and O 9
atoms.

Electronic states of formaldehyde

 n  p*(T) occur at 397 nm (green-
The lowest energy yellow)
electronic transition of formaldehyde  n  p*(S) occur at 355 nm
promotes a nonbonding (n) electron (colorless)
to the anti-bonding pi orbital (π*).

Two possible transitions, depending

on the spin quantum numbers in the
excited state:
The state in which the spins are
antiparallel is called a singlet
state (S1)
and if the spins are parallel, we have
a triplet state (T1).

Excited electron keeps Excited electron

direction of spin, changes direction of
Pairing stays the same spin
10

5
 Fundamentals of Spectrophotometry
What Happens When a Molecule Absorbs Light?

Infrared and Microwave Radiation

 Not energetic enough to induce electronic transition

 Change vibrational, translational and rotational motion of the molecule

- The entire molecule and each atom can move along the x, y, z-axis
- When correct wavelength is absorbed,
 Oscillations of the atom vibration is increased in amplitude
 Molecule rotates or moves (translation) faster
Vibrational States of Formaldehyde

Energy: Electronic >> Vibrational > Rotational

What Happens When a Molecule Absorbs Light?

Combined Electronic, Vibrational and Rotational Transitions

 Absorption of photon with sufficient energy to excite an electron will also cause
vibrational and rotational transitions
 There are multiple vibrational and rotational energy levels associated with each
electronic state
- Excited vibrational and rotational states are lower energy than electronic state
 Therefore, transition between electronic states can occur between different
vibrational and rotational states

Relaxation Processes from Excited State

 There are multiple possible relaxation pathways
 Vibrational, Rotational relaxation occurs through collision with solvent or
other molecules
- Energy is converted to heat (radiationless transition)
 Electronic relaxation occurs through the release of a photon (light)

6
 What happens to absorbed energy
Intersystem crossing
Internal conversion (radiationless transition)
(radiationless transition)

Phosphorescence
Fluorescence
Absorbance

h1 h2

13

After an absorption process, the system is at the S1 level, several events can happen:

Internal conversion (IC): The molecule could enter a highly excited vibrational level
of S0 having the same energy as S1. From this excited state, the molecule can relax
back to the ground vibrational state and transfer its energy to neighboring molecules
through collisions. This radiationless process is labeled R1. If a molecule follows the
path A–R1–IC–R2, the entire energy of the photon will have been converted into heat.

A; Absorption

Intersystem crossing
Internal conversion (radiationless
(radiationless transition)
transition)
Absorbance (A)

Phosphorescence
Fluorescence

h h
1 2
14

7
Intersystem Crossing (ISC):

The molecule could cross from an S1 state into an excited vibrational level of T1. After
the radiationless vibrational relaxation R3, the molecule finds itself at the lowest
vibrational level of T1.
From here, the molecule might undergo a second intersystem crossing to S0, followed
by the radiationless relaxation R4. All processes mentioned so far simply convert light
into heat.

Intersystem crossing
Internal conversion (radiationless
(radiationless transition)
transition)
Absorbance (A)

Phosphorescence
Fluorescence

h h
1 2
15

Fluorescence (F):
A molecule could also relax from S1 to S0 by emitting a photon. The radiational transition
S1→S0 is called fluorescence. Typical lifetimes of fluorescence processes are 10−8 to 10−4 s
(fast process).

Phosphorescence (P): A molecule could also relax from T1 to S0 by emitting a photon. The
radiational transition T1→S0 is called phosphorescence. Typical lifetimes of fluorescence
processes are 10−4 to 102 s, because the transition involves a change in spin
quantum numbers (2 unpaired electrons to 0 unpaired electrons), which is improbable!

Intersystem crossing
Internal conversion (radiationless
(radiationless transition)
transition)
Absorbance (A)

Phosphorescence
Fluorescence

h h
1 2
16

8
 Fundamentals of Spectrophotometry
What Happens When a Molecule Absorbs Light?

5.) Fluorescence and Phosphorescence

 Relative rates of relaxation depends on the molecule, the solvent,
temperature, pressure, etc.
 Energy of Phosphorescence is less than the energy of fluorescence
- Phosphorescence occurs at a longer wavelengths than fluorescence
 Lifetime of Fluorescence (10-8 to 10-4 s) is very short compared to
phosphorescence (10-4 to 102 s)
 Fluorescence and phosphorescence are relatively rare