1

Required Reading: FP Chapter 3

Suggested Reading: SP Chapter 3
Atmospheric Chemistry
CHEM-5151 / ATOC-5151
Spring 2005
Maggie Tolbert & Jose-Luis Jimenez
Lecture 5: Spectroscopy and
Photochemistry I
Outline of Next Two Lectures
Today
Importance of spectroscopy & photochemistry
Nature of light, EM spectrum
Molecular spectroscopy
Thursday
The Sun as a radiation source
Light absorption
Atmospheric photochemistry
2
Importance of Spectroscopy and Photochemistry I
Most chemical processes in the atmosphere are initiated by
photons
Photolysis of O
3
generates OH the most important atmospheric oxidizer:
O
3
+ hv O
2
+ O(
1
D)
O(
1
D) + H
2
O 2 OH
Solar photodissociation of many atmospheric molecules is often much faster
than any other chemical reactions involving them:
CF
2
Cl
2
+ hv CF
2
Cl + Cl (photolysis of CFCs in the stratosphere)
HONO + hv OH + NO (source of OH in the troposphere)
NO
2
+ hv O + NO (source of O
3
in the troposphere)
NO
3
+ hv O
2
+ NO or O + NO
2
(removal of NO
3
generated at night)
Cl
2
+ hv Cl + Cl (source of Cl atoms)
H
2
CO + hv H
2
+ CO or H + HCO (important step of hydrocarbon
oxidation)
etc.
Importance of Spectroscopy and Photochemistry II
Absorption of solar and earth radiation by
atmospheric molecules directly influences the
energy balance of the planet
Greenhouse effect (CO
2
, H
2
O, N
2
O, CFCs)
Stratospheric temperature inversion (O
3
photochemistry)
Spectroscopy of atmospheric molecules is used to
detect them in situ
OH is detected via its electronic transition at 310 nm
NH
3
is detected via its fundamental vibrational transition at
1065 cm
-1
, etc.
3
Solar Radiation: Initiator of Atmos. Reactions
Average thermal energy of collisions:
~ RT = 8.3 J mol
-1
K
-1
x T
RT = 2.5 kJ mol
-1
@ 300 K
Energy of photons (E = hv):
300 nm photon = 380 kJ mol
-1
600 nm photon = 190 kJ mol
-1
Typical bond strengths:
D
0
(O
2
) = 495 kJ mol
-1
D
0
(Cl
2
) = 243 kJ mol
-1
C-H, O-H, C-O ~ 400 kJ mol
-1
Atmospheric chemistry on Earth is driven by
photolysis, not by thermal excitation!!!
From S. Nidkorodov
What is light?
Dual nature
Photon: as particle
Energy but no
mass
As wave: electric
and magnetic
fields oscillating in
space and time
Wavelength,
frequency
c ~ 3 x 10
9
m/s
From F-P&P
Discuss in class: at a fundamental physical level,
why are molecules capable of absorbing light?
4
The Electromagnetic Spectrum
Units used for photon energies and wavelengths:
1 eV = 8065.54 cm
-1
= 96.4853 kJ/mol = 23.0605 kcal/mol =
11604.4 K
1 = 0.1 nm = 10
-10
m; micron = 10
-6
m = 1000 nm
Solve in class: Calculate the energy, frequency, and
wavenumber of a green photon ( = 530 nm).

v
v

1

c

=
=
=
v
h E
(wavenumber)
Types of radiation important in lower atmosphere
Ultraviolet and visible radiation ( = 100-800 nm)
Excites bonding electrons in molecules
Capable of breaking bonds in molecules (
photodissociation)
Ultraviolet photons ( = 100-300 nm) have most energy, can
break more and stronger bonds. We will pay special attention
to them.
Infrared radiation ( = 0.8 - 300 m)
Excites vibrational motions in molecules
With a very few exceptions, infrared radiation is not energetic
enough to break molecules or initiate photochemical
processes
Microwave radiation ( = 0.5 - 300 mm)
Excites rotational motions in molecules
5
v', J',
v", J",
E
p
h
o
t
o
n
Fundamentals of Spectroscopy
Molecules have energy in translation,
vibration, rotation, and electronic state
Translation (= T) cannot be changed directly
with light
We will focus on the other 3 energy types
Molecule can absorb radiation efficiently
if:
The photon energy matches the energy
spacing between molecules quantum levels
Optical transition between these quantum
levels is allowed by selection rules
Forbidden transitions can occur but are
weaker
Vibrational Energy & Transitions
Bonds can be
viewed as
springs
Energy levels are
quantized,
E
v
= hv
vib
(v+1/2)
v
vib
is constant
dependent on
molecule
v = 0, 1, 2 is
vibrational
quantum number
From F-P&P
6
Vibrational Energy Levels
Ideally: Harmonic Oscillator
Restoration force of spring
follows Hookes law: F= k Ax
E
v
= hv
vib
(v+1/2), v = 0, 1, 2
Energy levels are equally spaced
Really: Anharmonic oscillator
Restauration force rises sharply
at small r, bond breaks at large r
Vibrational quantum levels are
more closely spaced as v
increases
( ) ( ) ( ) ... y h x h h E
e e vib
+ + + + + =
3 2
2
1
2
1
2
1
v v v v v
From F-P&P
Vibrational Selection Rules
For ideal harmonic oscillator
Av = 1
For anharmonic oscillator
Av = 2, 3 weaker overtone transitions can occur
At room T most molecules at v = 0
Energy spacing of levels is large (~1000 cm
-1
)
v' = 0 v = 1 is by far strongest
For purely vibrational transition
Absorption of light can occur if dipole moment
changes during vibration. E.g. HCl, CO, NO
Homonuclear diatomics, e.g. O
2
, N
2
dont have v.t.
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Infrared Active and Inactive Modes
Only vibrational modes
that change the dipole
moment can interact
with light and lead to
absorption
CO
2
is infrared active,
but not all of its modes
are
Rotational Energy and Transitions
If molecule has permanent dipole
Rotation in space produces oscillating electric field
Can interact with lights fields and result in absorption
Only heteronuclear molecules
Rigid rotor
No simultaneous vibration
Allowed energy levels:
Nonrigid rotor
Spacing increases with J
Spacing between levels small, many levels are populated
... ) 1 ( ) 1 (
2 2
+ + + = J DJ J BJ E
rot
2
2 1
2 1
2
2
1
8
) 1 (
R
m m
m m
I
I
h
B
cm J BJ E
-
rot
+
= =
+ =
where
t
8
Rotational level manifolds for
different vibrational quanta
overlap with each other
Example: Ground Electronic State of HF
HF molecular constants
9 B
v=0
= 20.557 cm
-1
(rotational constant)
9 v = 4138.32 cm
-1
(harmonic frequency)
9 vx
e
= 89.88 cm-1 (anharmonicity)
v
) 1 (
h E
J BJ E
E E E
vib
rot
vib rot total
~
+ ~
+ =
Possible
rovibrational
transition:
v=0 v=1
J=14 J=15
From S. Nidkorodov
Vibration-rotation of HCl
Molecules vibrate and rotate
simultaneously
From F-P&P
9
Electronic Energy and Transitions
Several additional quantum numbers
A: related to electronic angular momentum
S: spin number
Multiplicity = (2S + 1)
Mult = 1, 2, 3 are referred to as singlet, doublet, triplet
Most stable molecules have singlet ground states
O
2
has triplet ground state, important exception
O = | A+ E|
E = +S, S-1, . , -S
g or u states
+ or - states of E
More complex selection
rules involving these numbers:
From F-P&P
Electronic Transitions (ETs)
Molecules can undergo an
ET upon absorption of an
appropriate photon
Simultaneous vibrational
and rotational transitions
No restriction on Av, many
vib. trans. can occur
AJ = -1, 0, +1
P, Q, and R branches
Frank-Condon principle
Time for ET so short (10
-15
s) that internuclear distance
cannot change
vertical transitions
From F-P&P
10
Potential Energy Curves for an ET
At room T, v''=0
Prob of transition
proportional to
product of vib.
wavefucntions
Transition to v'=4
in upper
electronic state
most intense
From F-P&P
Repulsive States
No minima in PE
vs r curves
Dissociation
occurs
immediately after
absorption of light
From F-P&P
11
More complex case & Predissociation
Some repulsive and some
non-repulsive upper elec.
states
Example
Trans. to R causes
immediate dissociation
Trans. to E can lead to
dissociation if cross over to
state R occurs
Predissociation
If high enough energy,
trans. to E can yield
A + B*
From F-P&P
1. Number of vibrations increases to s = 3N-6 (s = 3N-5 for linear molecules),
where N is the number of atoms in the molecule:
H
2
O: N = 3 s = 3
C
6
H
6
: N = 12 s = 30
C
60
: N = 60 s = 174
2. Three independent axes of rotation, each characterized by its own rotational
constant (A, B, C):
3. Complexity of the absorption spectrum increases very quickly with N. New
types of bands become possible:
Asymmetric tops A = B = C
H
2
O molecule, meat grinder
Prolate symmetric tops A < B = C
CH
3
F molecule; a pencil
Oblate symmetric tops A = B < C
CH
3
radical, planet Earth
a
b
c
a
b
c
b
a
c
9 Sequence bands: one vibration excited while maintaining excitation in another vibration (allowed)
9 Combination bands: two different vibrations excited simultaneously (forbidden in harmonic approximation)
9 Overtone bands are also possible, just like for diatomic molecules (forbidden in harmonic approximation)
Polyatomic Molecules
From S. Nidkorodov
12
Water has s = 3
vibrations:
v
1
= 1595 cm
-1
v
2
= 3652 cm
-1
v
3
= 3756 cm
-1
It is a strongly
asymmetric top:
A = 27.9 cm
-1
B = 14.5 cm
-1
C = 9.3 cm
-1
Overtone and
combination
bands are
relatively intense
(only selected
bands shown in
the graph)
Example: Vibrational Spectrum of H
2
O
From S. Nidkorodov
v
1
+v
3
combination band
shown a pure
vibrational transition.
No obvious pattern in the
spectrum (this is very
typical for asymmetric
tops).
Sample Near-IR Spectrum of H
2
O
From S. Nidkorodov
13
From Wayne
Pathways for Loss of e
-
Excitation
Photophysical
processes
Lead to emission
of radiation
Energy converted
to heat
Read details in
book
Photochemical
processes
Dissociation,
ionization,
reaction,
isomerization
Photochemical processes
Can produce new chemical species
Photodissociation
most important by far
E.g. sole source of O3 in troposphere:
NO
2
(X
2
A
1
) + hv (290 < < 430 nm)
NO(X
2
P) + O(
3
P)
Others: intramolecular rearrangments,
photoisomerization, photodimerization, H-atom
abstraction, and photosensitized reactions
Reminder: photochemistry drives the chemistry
of the atmosphere
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Quantum Yields (|)
Relative efficiency of various photophysical and
photochemical processes:
E.g.: NO
3
+ hv NO
3
*
(3)
NO
3
*
NO
2
+ O (4a)
NO + O
2
(4b)
NO
3
+ hv (4c)
and so on
|
i
Are wavelength dependent, all important at different
absorbed photons of number Total
i process by proceeding molecules excited of Number
=
i
|
absorbed photons of number Total
formed molecules NO of Number
2
4
=
a
|
Quantum Yields II
From F-P&P