Fundamentals of
spectroscopy
1
Properties of Light
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
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 -).
5
Fundamentals of Spectrophotometry
What Happens When a Molecule Absorbs Light?
6
What happens to absorbed energy
Intersystem crossing
Internal conversion (radiationless transition)
(radiationless transition)
Phosphorescence
Fluorescence
Absorbance
h1 h2
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?