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 Å = 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 (ì = 530 nm).
ì
v
v
ì
1

c

=
=
=
v
h E
(wavenumber)
Types of radiation important in lower atmosphere
• Ultraviolet and visible radiation (ì = 100-800 nm)
– Excites bonding electrons in molecules
– Capable of breaking bonds in molecules (¬
photodissociation)
– Ultraviolet photons (ì = 100-300 nm) have most energy, can
break more and stronger bonds. We will pay special attention
to them.
• Infrared radiation (ì = 0.8 - 300 µm)
– 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 (ì = 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 molecule’s 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 Hooke’s 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 hȞ 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 ĺv‘ = 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
don’t have v.t.
7
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 light’s 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 (
hȞ 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 < ì < 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
14
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 ì
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

Sign up to vote on this title
UsefulNot useful