2.

2 INTERACTION OF
ELECTROMAGNETIC
RADIATION WITH ATOMS
AND MOLECULES

2.1 NATURE OF ELECTRO­ Ey =A sin(wt - kx) (2.1) Figu

alon
MAGNETIC RADIATION
and
lt was Maxwell, in 1855, who first concluded that H0 =A sin(wt - kx) (2.2)
visible radiation can be regarded as an electro­
magnetic disturbance in the form of waves, and piar
Equations (2.1) and (2.2) are the equations of
we know that ali electromagnetic radiation can tion
motion for plane-polarized radiation travelling
be regarded in this way. lt may also be con­ of ¡
along the x-axis and show that both fields
sidered as consisting of particles (photons) but, Fig1
oscillate sinusoidally with a radial frequency w.
in this book, it will be primarily the wave The quantity k determines the phase ofthe waves
picture with which we shall be concerned. and the fact that it is the same for Ey and H2
The kind of electromagnetic radiation which means that the two fields always oscillate in phase 2.2
perhaps best illustrates its nature is that which with each other; for example, Ey = H2 = A when
is plane-polarized.t As the word electromag­ t = O at x = O. Equations (2.1) and (2.2) show
netic implies, ali electromagnetic radiation is of also that the fields have the same amplitude and Wh
a dual character: it has an electric and a frequency. Figure 2.1 illustrates all these proper­ gas,
magnetic component. The electric component ties of plane-polarized radiation. be:
is in the form of an oscillating electric field, Although the dual electric-magnetic character ma:
whose magnitude and direction is specified by of electromagnetic radiation is of great funda­ is 1
the vector E, the electric field strength. The mental importance, we shall find that, in its exa
magnetic component is in the form of an interaction with atoms and molecules, it is the sca1
oscillating magnetic field, whose magnitude oscillating electric field which is more often (f01
and direction are specified by the vector H, involved than the magnetic field. For example, abs
the magnetic field strength. In plane-polarized if radiation falls on a photographic plate it may the
radiation these two vectors oscillate in mutually cause blackening; if it falls on a fluorescent ligt
perpendicular directions. If the directions in screen it may cause fluorescence of the material J
which the electric and magnetic vectors oscillate of which the screen is made; and ifit falls on the res<
are y and z, respectively, then retina of the eye it may cause a signa! to be pla
transmitted to the brain. Ali these effects are oft
due to interaction of the detector with the mo
electric vector only. rá.d
Because the- electric vector is generally the pre
t Also known as linearly polarized. more important, the plane of polarization of un<
 2.2 ABSORPTION AND EMISSION PROCESSES 33

(2.1) Figure 2.1 The electric and magnetic components of plane-polarized electromagnetic radiation travelling
along the x-axis

(2.2)
plane-polarized radiation is defined conven- frequency, from the radiation. Subsequently the
ns of
tionally as the plane containing the direction energy is lost by emission or perhaps transferred
!lling
of propagation and of the electric vector: in to another system.
fields
Figure 2.1 this is the xy-plane. The process of absorption by an atom or
:y w.
molecule is illustrated by (a) in Figure 2.2, where
,aves
m and n are stationary states. The following
d H2
discussion applies whether the states are electro-
,hase 2.2 ABSORPTION ANO
nic, vibrational, rotational or whatever.
.vhen EMISSION PROCESSES
Although states m and n are stationary states,
show
and therefore independent of time, the absorp-
: and When electromagnetic radiation falls on a
tion process is not instantaneous: it takes a
Jper- gaseous, liquid or solid material, which may
period of time t 1 given by
be atomic or molecular in nature, the radiation
acter may be (i) transmitted (for example, visible light
t 1 = v- 1 = (cií)- 1 (2.3)
mda- is transmitted by water); (ii) scattered (for
n its example, small particles suspended in water
s the scatter blue light preferentially); or (iii) absorbed En n
Jften (for example, the red part of visible light is
nple, absorbed by copper sulphate solution, causing
may the remaining transmitted light, which is white (al (b) (el
scent light minus red light, to appear blue). El
terial
n the
o be
Justas a wine glass may be caused to vibra te, or
resonate, in sympathy with a musical instrument
playing a note containing the resonance frequency
Em lnduced
¡ ¡
lnduced Spontaneous
m
s are of the glass, so resonance may occur if an atom or
absorpt1on emiss1on emiss ion
the molecule is placed in the path of electromagnetic
radiation containing certain frequencies . The first Figure 2.2 Illustration of the absorption and
r the process which the glass, or the atom or molecule, emission processes which may take place between
,n of undergoes is to absorb energy, at the resonant two stationary states m and n
34 2 INTERACTION OF ELECTROMAGNETIC RADIATION WITH ATOMS AND MOLECULES 2.2 ABSORPTIC
where the frequency v, or wavenumber v, is the Boltzmann factors of ali the states in the emits energy i
related to /1.E, the energy separation of the system. the same ene
states, by An alternative way of discussing populations presence of th
is in terms of energy levels rather than sta\~s._ emission to o
/1.E = E 11 - E 111 = hv = hcv (2.4) This affects the discussion when degenerate when the phen
states are involved, i.e. states having differeni an analogy car
For example, if an absorption process occurs at wave functions but the same energy. Thus, if an seeding of a r:
a wavelength of 600 nm, in the green region of energy leve! is g-fold degenerate then the ratio of spontaneou
the visible spectrum, then of N 11 , the number of atoms or molecules with (see later for
energy E11 , to Nm, the number with energy Em, is emission), but
t¡ = (cv)- I =},je= 2.ÜÜ X 10- IS S (2.5) given by for it to do so
suitable crysta
This time is clearly very short, but not N,,/N111 = (g / g exp(-/1.E/ kT)
11 111 ) (2.8) shower of rair
negligible, and we might ask what happens to happen.
and equation (2.7) becomes
the wave function describing the system during An atom o
this time. What happens is self-evidently time- similarly be ir
N 11 / ¿N¡=
dependent and the quantum mechanical presence of su
description involves the use of equation (1.37), crystals in see,
g11 exp(-E11 / kT)/ ¿ g¡ exp(-E,/kT) (2.9)
the time-dependent Schrodinger equation. We emission procc
shall not pursue this any further except to say or molecule
tha t, during the time t 1, the stystem evolves Note that the partit1on / function, equation
from one which is described by the stationary L,¡g; exp(-E,/kT), of equation (2.9) is equal
state wave function t/; m, through intermedia te to that of equation (2. 7). 1V
states involving mixtures of wave functions, to From equations (2.6)- (2.9) it is clear that the
one described by the stationary state wave equilibrium populations of state~ decrease where M* is
function t/;w rapidly (exponentially) as the energy increases. state n and he
At equilibrium the populations N 11 and Nm of In certain circumstances, for a particular pair a wavenumbe
the upper and lower states, respectively, are of states in a particular atom or molecule, it is equation (2.4:
related, according to the Boltzmann distribu- possible to achieve a population inversion in Justas we 1
tion law, by which N 11 > Nm. This leads to the possibility of (2.1 O) an ind1
the production of lasers, which will be discussed by the radia
N 11 / N 111 = exp(-/1.E/ kT) (2.6) in Chapter 8. process (a), i
If the population distribution in the two-level since, of cour
where /1.E is given by equation (2.4), k is the system in Figure 2.2 is initially the equilibrium of radiation.
Boltzmann constant and T is the temperature in one given by equation (2.6) the absorption
kelvins. In a system having many stationary process (a) disturbs this equilibrium by increas-
states, equation (2.6) gives the ratio of the ing N 11 and decreasing N 111 • When the source of
populations of any pair of states m and n. The The secon,
radiation which excites the atoms or molecules
probability of finding an atom or molecule in 2.2, is called
from m to n is removed equilibrium will be
state n in a multistate system is given by process
restored over a period of time by loss of energy
/1.E. This loss may occur in various ways, which
N,, / ¿ N¡ = exp(-E /kT)/¿ exp(-E,/kT)
11
will be discussed in Section 2.3, but the one which
concerns us here is the reverse of absorption, In this case
(2.7) namely the emission of radiation of energy /1.E. presence of r
Emission may take place by two different The rateo
The denominator of the right-hand side of this processes. The first of these is known as induced state,- áN11 7c
equation is the partition function- the sum of or stimulated emission in which the system proportional
:CULES 2.2 ABSORPTION AND EMISSION PROCESSES 35
in the emits energy in the presence of radiation of state and to the radiation density, p(v), which is
the s_ame energy. The requirement of the the density of radiation of wavenumber v falling
lations presence of this radiation in order to induce on M; therefore, we have
sta!es.. emission to occur may seem rather curious
:nerate when the phenomenon is first encountered but (2.13)
fferent an analogy can be drawn between this and the
s, if an seeding of a rain cloud. The cloud is capable where B nu1- i_s_ the Einstein coefficient for induced
� ratio of spontaneously emitting a shower of rain absorption. Similarly, the change of population
:s with (see later for a discussion of spontaneous due to induced emission is
E111 , is emission), but conditions may not be suitable
for it to do so. But if the cloud is seeded with dN,, /dt = -N11 B,, 111p(v) (2.14)
suitable crystals it may be induced to emit a
(2.8) and that due to spontaneous emission is
shower of rain when otherwise this would not
happen.
dN,, /dt = -N,, A ,,m (2.15)
An atom or molecule in the state n may
sipiilarly be induced to emit radiation by the where B ,,m and Á nm are the Einstein coeffi­
presence of suitable photons, analogous to the cients for induced and spontaneous emission,
(2.9) crystals in seeding the rain cloud. The induced respectively. The coefficients were introduced in
emission process, (b) in Figure 2.2, in an atom 1917 by EinsteÍn, who was also the first to
or molecule M can be represented by the propose that spontaneous emission may occur,
1ction, equation
equal in addition to induced emission, and to show
that
M* + hcv � M + 2hcv (2.1O)
1at the
crease where M* is an excited atom or molecule in Bmn = Bnm (2.16)
eases. state n and hcv is a photon of radiation having
In the presence of radiation of wavenumber v
Lr pair a wavenumber related to the energy levels by
ali three processes are going on at once and the
�, it is equation (2.4).
overall rate of change of the population of the
on m Just as we have called the process of equation
upper state is
lity of (2.10) an induced process, because it is induced
:ussed by the radiation, so strictly we should call
dN,, /dt = (N111 N,,)B,,,,,p(v) - N11 A 11111 (2.17)
process (a), in Figure 2.2, induced absorption
-

>-leve! since, of course, this also requires the presence If the source of radiation is removed then
brium of radiation. Induced absorption is the process p(v) = O, the rate becomes (-N11 A 11m ) and only
·ption spontaneous emission occurs.
creas­ M+hcv � M* (2.11) When the states n and m have their equili­
rce of
The second em1ss10n process, (c) in Figure brium Boltzmann populations, dN11 /dt = O and
ecules
2.2, is called spontaneous emission and is the
ill be
process
(Nm - N,,)B 11111 p(v) - N,, A,, m =O (2.18)
nergy
which Nm and N,, are related, according to equation
M* � M +hcv (2.12)
which (2.6), and the radiation density of a black body
ption, In this case M* spontaneously, without the has been shown, by applying Planck's quantum
fiE. presence of radiation, emits a photon. theory to the oscillators emitting the radiation,
ferent The rate of change of population of the upper to be given by
foced state; aNn /dt, due to induced absorption is
ystem proportional to the population N111 of the lower p(v) = 8nhcv 3 [exp(hcií/kT)- 1r 1 (2.19)
36 2 JNTERACTION OF ELECTROMAGNETIC RADIATION WJTH ATOMS AND MOLECULES 2.2 Afü

From equations (2.6), (2.18) and (2.19), it H"CD e:> ,......-H (a)
follows that e-e
H/c:> CD"'H
A,,m = 8nhcv 3 B 11111 (2.20)
(al (b)
This equation illustrates the important point
that spontaneous emission increases rapidly in Figure 2.3 (a) A n and (b) a n* orbital of ethylene
importance relative to induced emission as the
wavenumber (or frequency) increases because
{b)
of the v3 dependence of A 11m.
The magnitudes of the Einstein coefficients
are dependent on the wave functions of the two (this is given by equation 2.22 referred to a
combining states and, in particular, on what is particular axis) for the integral to be non-zero.
called the transition moment for the transition Ethylene has no dipole moment in either of
the
between the state m and n. For absorption or states m or n, owing to the symmetry of the
emission involving the electric component of electronic charge in both the n- and n*-orbitals, {e)
the radiation, which is most often the case, the but the transition moment is non-zero. The
transition moment Rm11 , a vector quantity having square of the magnitude of the transition
magnitude and direction, is given by moment vector, IR11m¡ 2 , is the transition prob-
ability and is related to the Einstein coefficient Figure:
R"m -- I ,!,* ,/, d r
'1'11µ'!'111 (2.21)
Bnm by A broa,
band w
(2.23)
where µ is also a vectort and is the electric
dipole moment operator. lt is given by range.
Quantum mechanical calculation may be used absort
to estímate the transition probability for a the C(
(2.22) particular pair of states; then B,,m follows from absort
equation (2.23) and A 11111 from eq-µation (2.20).
where q; and r; are the charge and pos1tton But how are experimental intensity measure-
vector, respectively, of the ith particle. The ments related to Einstein coefficients?
transition moment can be thought of as the Consider a simple absorption experiment,
shown diagrammatically in Figure 2.4(a), in where
oscillating electric dipole moment caused by a
which radiation of intensity / 0 , and a con- molar
transition from state m to state n.
tinuous range of wavelengths, passes through a numb€
As an illustration of this, consider a transi-
cell of length l containing a sample in the liquid has d
tion between two electronic states m and n in
phase with a concentration e and which absorbs and ti
ethylene in which an electron is transferred
the incident radiation over a range of wave- To th
from the n-orbital in Figure 2.3(a) to the n*-
orbital in Figure 2.3(b). Clearly there is charge numbers v1 to v2 . If the intensity of radiation of Figurt
movement during the transition, an oscillating wavenumber v emerging from the cell is /, then value
the quantity log 10 (/0 / I) is called the absor- which
electric dipole moment is set up during the
transition from state m to state n, and the bance, A, which is a function of v. A plot of A measu
integral in equation (2.21) is non-zero. How- against v, an example of which is shown in Howe
ever, note that it is not necessary for the Figure 2.4(b), is one way of presenting the
molecule to have a permanent dipole moment absorption spectrum. In a liquid-phase experi-
1Until 1
ment the absorption in, say, the visible region of and sm
the spectrum using visible radiation is typically the use
1The symbol p may be used instead of µ. broad, extending over a large wavenumber equatic
:ULES 2.2 ABSORPTION ANO EMISSION PROCESSES 37
ignores the width of the absorption and would
(a) give the same intensity for the broad absorption
in Figure 2.4(b) as for the narrow absorption in
Figure 2.4(c). A more accurate measure of
intensity is the area under the absorption curve,
i.e. J;2 e(v) dv. If the states m and n are
1ylene
~
u separa1ted by an energy difference which is
e
11] large enough for Nn to be very much less than
{ b) .e
o
... Nm, then induced emission will be negligible
V)
.e compared with absorption; under these condi-
<
~ tions the area under the absorption curve is
~1
to a related to B11m by
-zero.
ofthe
(2.25)
)f the ~
u
e
bitals, (e) 11]

. The
.e
...o where v11m is the average wavenumber of the
V)

1sition .e transition and NA is the Avogadro constant.:I:

prob- <"-=-~~~==------~ If the absorption is due to a transition
"ficient Figure 2.4 (a) A simple absorption experiment. (b) between electronic states, a quantity .fmn, the
A broad absorption band. (e) A narrow absorption oscillator strength of the transition, is often
band with the same Bmax as in (b) used . It is related to the area under the curve by
(2.23)
range. According to the Beer- Lambert law, the
e used absorbance is proportional to the length of
for a the cell and to the concentration of the
s from absorbing sample, as expressed in the equation where me is the mass and e the charge of the
2.20). electron; fnm is a dimensionless quantity and
:asure- is the ratio of the strength of the observed
Á = log10Uol !) = e(v)cl (2.24)
transition to that of an electric dipole transition
·iment, between the two states of an electron oscillating
(a), in where e is the molar absorption coefficientt or in three dimensions in a harmonic way: fnm can
a con- molar absorptivity and is a function of wave- be calculated from i/1 11 and i/lmand its maximum
ough a number. Since absorbance is dimensionless, e value is usually 1.
: liquid has dimensions of (concentration x length)- 1 Transition probabilities can be obtained from
. are very o ften mo1-1 d m 3 cm -1 .
and t he umts
,bsorbs B,,111 using equation (2.23). They are concerned
wave- To the maximum value of the absorbance in with the very important topic in spectroscopy of
.tion of Figure 2.4(b) there corresponds a maximum selection rules. These rules tell us whether a
/, then value of the molar absorption coefficient, Bmax, transition between two states m and nis allowed
absor- which is sometimes used as an approximate or forbidden and, in terms of transition prob-
)t of A measure of the total absorption intensity. abilities, this means that
)Wn in However, this is only approximate because it
ng the
expen- lThis equation is often given in a slightly different form to
tuntil recently E was called the molar extinction coefficient take account of the fact that the usual units of s(ii) are
:gion of and sometimes the word 'decadic' was inserted to indicate mo1- 1 dm3 cm- 1; but equation (2.25) is always valid pro-
ypically the use of the base of 1O rather than e for the logarithm in vided a self-consistent set of units is used for the various
number equation (2.24). physical quantities.
38 2 JNTERACTION OF ELECTROMAGNETIC RADIATION WITH ATOMS AND MOLECULES 2.3 LINE W

IR"ml 2 = O forbidden
¡R m¡2 =fa O allowed
11
(2.27)
.
X

1
1 '
'
'
this means
2n/ n abou1
which is inc
(a) - - --- O ,:·' O- ----z In the case
,' 1
Strictly we must speak of electric dipole allowed Formaldeh
or electric dipole forbidden transitions, if we are
'
(o-) which
concerned with interaction of the electric vector through e
of the radiation, and magnetic dipole allowed or X
configurati
forbidden transitions for interaction of the t
H 1 ,' gina} one:
magnetic vector. There are also, as we shall ........ 1'

see later, the important Raman selection rules

(b) ----~e
/
. ,: .
,,
0-----z Figure 2.51
the other
and the less important electric quadrupole H' ,." : axis perpe1
/ 1
selection rules. Normally, unless we are con- Y' taken to 1:
cerned with Raman or spin resonance spectro- sysJem_js t
scopy, it can be assumed that when we speak of In such a
allowed or forbidden transitions we are refer- H R'.t =I= O ,
ring to electric dipole selection rules unless it is polariza tic
1
stated otherwise. (el ( one of the
The electric dipole moment is a vectorµ and
has components along the cartesian axes
/\'sr In a me
as CHBrc
F CI
cartesian
Figure 2.5 (a) Polarization directions of transition therefore 1
moments in the oxygen molecule. (b) Polarization is not con
directions in the formaldehyde molecule. (e) The These e
(2.28) polarization directions are not restricted by symme-
the direct
µz = L q¡ Z¡
try in the bromochlorofluoromethane molecule
illustrate
of symm
symmetry
where q¡ is the charge on the ith particle
trans1t10n in such a system the trans1tion 5.2.2.
(electron or nucleus) and X¡, y¡ and z¡ are its
coordinates. Therefore, it follows that the moment vector is not polarized in any particular
transition moment can be resolved into three direction.
components: A diatomic molecule, such as oxygen, has 2.3 LI
lower symmetry than an atom. If we take the TE

R xl//11 -- I·'·* .,.

'1' nµx'l'm dX
z-axis to be the line of the nuclei, as shown in
Figure 2.5(a), then for an allowed transition Even une
observati
either R 2 =fa O and Rx = Ry = O and we say that
Rt = J ¡/;;,µyij;m dy (2.29) the transition moment is polarized along the z- such as n

R ll/11
z -- I·'·* .,.
'f'nµz\f' m dZ
axis, or R 2 = O and Rx = Ry =fa O, in which case
the transition moment is polarized in the xy-
plane: the symmetry of the molecule results in
infinitely
reproduc
We sh
and the transition probability is related to these the x- and y-axes being indistinguishable. mentatio
components by A molecule with still lower symmetry is
formaldehyde, which is planar and is shown in
Figure 2.5(b). In this molecule the directions of trt is a tri,
(2.30)
refer to a
the cartesian axes are defined by symmetry. The method of
In a spherically symmetrical system, such as C 2 axis is conventionally taken as the z-axis. If, does when
an atom, Rx = Ry = R 2 and for an allowed in general, a molecule has an n-fold axis ( C11 ) as a peak
=ULES 2.3 UNE WIDTHS OF TRANSITIONS 39

this means that rotation of the molecule by

2n/n about that axis produces a configuration
which is indistinguishable from the original one.
In the case of the z-axis of formaldehyde, n = 2.
Formaldehyde also has two planes of symmetry 1
QJ
(o") which means that reflection of the nuclei u
through either of these planes produces a e
ro
configuration indistinguishable from the ori- ..o
c...
ginal one: these are the xz- and yz-planes in o
V)
Figure 2.5(b) and they define the directions of ..o
the other cartesian axes. Conventionally the <t:
axis perpendicular to the plane of the nuclei is
taken to be the x-axis. The origin of the axis
-v
system__ is the centre of gravity of the molecule.
In such a molecule if IRnm¡ 2 i= O, then either Figure 2.6 Typical line shape for a transition
R~m -¡: O or R;m i= O or R;m i= O and the observed in absorption
polarization of the transition moment is along
one of the axes and can never lie between them.
In a molecule with no symmetry at ali, such
as CHBrClF in Figure 2.5(c), none of the
itself be the limiting factor in the observed line
cartesian axes is defined by symmetry and
shape. For example, a slit of a spectrometer
1sition therefore the direction of the transition moment
rntion may be too wide or a diffraction grating may
is not confined at ali by symmetry.
) The not be of sufficiently high quality. In this
These examples of the possible restrictions of
•mme- section we shall assume that the experimental
the directions of transition moments serve to
method used to obtain the spectrum <loes not
illustrate one aspect of the great importance
impose any limitations on the line shape.
of symmetry in such problems. Molecular
Figure 2.6 illustrates a typical line shape for a
symmetry will be treated at length in Section
transition observed in absorption: absorbance
,ition 5.2.2.
(equation 2.24) is plotted against frequency (or
cular
wavenumber). In referring to a parameter which
is related to the width of the line we use the half
, has 2.3 LINE WIDTHS OF intensity line width, which is the width of the
e the TRANSITIONS line at half the maximum absorbance or,
Nn m
alternatively, the half width at half maximum,
,ition Even under the most favourable conditions for
abbreviated to HWHM and equal to 11v in the
, that observation, a transition between two states,
figure.
:hez- such as m and n in Figure 2.2, is not seen as an
There are severa! factors, other than instru-
L case infinitely sharp line t but there is a definite,
mental ones, which- may contribute to the
e xy- reproducible line shape.
observed line shapes and the most important
lts in We shall see in Chapter 3 that the instru-
are
mentation used for observing a spectrum may
ry 1S (1) natural line broadening;
Nn m (2) Doppler broadening;
ns of 1It is a trivial point, but worth noting here, that we often (3) pressure broadening;
. The refer to a 'line' in a spectrum irrespective of whether the (4) wall collision broadening;
method of observation causes it to appear as a line, as it
is. If, <loes when we use a spe.¡;troscope and the eye as detector, or (5) power saturation broadening;
(C,i) as a peak in a plot of intensity versus wavelength. (6) modulation broadening.
40 2 INTERACTION OF ELECTROMAGNETIC RADIATION WITH ATOMS AND MOLECULES 2.3 LJ]\

Within these categories there is a useful distinc- and is therefore larger than the half-life. We station:
tion between contributions to the line shape refer to r as the relaxation time or simply the finite. I
which are the same for every atom or molecule of lifetime of M* and it is the time taken for the represe
the sample- homogeneous line broadening- concentratioñ of M* to fa]] to 1/e times its b./;. If
and those which result from a statistical average initial value (e is the base of natural logarithms r due o
of a property which is not the same for ali atoms here). called -,
or molecules-inhomogeneous line broadening. There are various ways in which M* can resultir
decay to M by a first-order process. Often the width.
most important is spontaneous emission for For
2.3.1 Natural line broadening
which the rate constant is given by natura
Excited states which are populated in excess of From
their Boltzmann equilibrium population decay (2.36) 5.3 X 1
as a function of time. If m in Figure 2.2 is the b.v ;:: e
ground state of an atom or molecule M then where A 11111 is the Einstein coefficient for 16MH
decay of the excited species M* to its equili- spontaneous em1ss10n. Another important At t
brium concentration is commonly a first-order mechanism of decay is by transfer of energy in long li
process. This is analogous to any first-order collision processes, which will be discussed in of a
chemical reaction. The rate of disappearance of Sections 2.3 .3 and 2.3.4. If M* is an excited 10- 4_¡
M* is proportional to its concentration, giving electronic state then it may decay to a lower Fro1
excited state, between n and m, or to the ground that t
dN11 state m by a radiationless transition in which no Einste
-dt=kN11 (2.31) energy is radiated but the excess electronic A,,111 , e
energy is converted into vibrational energy. The
where k is the first-order rate constant (and not species M* may also undergo photochemical
to be confused with the Boltzmann constant). reaction
Integrating from time zero to t gives
M* ---+ products (2.37) Since
In [N11 (t) / N,,(O)] = -kt (2.32)
Collisional decay is second order but the other
or processes are first order, so we now have

N,,(t) = N,,(O) exp(-kt) (2.33) k = Anm + k,t + kphoto + · · · + kco11 [M] + when
(2.38) equa1
For a first-order reaction, particularly a radio- the u
active decay process, we sometimes refer to the where k, 1, kphoto and kcoll are the rate constants (2.39
half-life, t 21, which is the time after which the for decay by radiationless transitions, photo-
concentration has decreased to half of its initial chemical reaction and collisions, respectively.
value. From equation (2.32) it follows that [M] is the concentration of M, or M*, and
kc011 [M] is a pseudo-first-order rate constant.
In 2 0.693 The form of the Heisenberg uncertainty The
{¡ =-=-- (2.34) natt
2 k k principie given in equation (1 .29) gives the
uncertainty b.E of the energy of a state with a part
In spectroscopy we more often use the quantity lifetime r as the
r , which is the reciproca! of the first-order rate leve
constant: (2.39) exci
exc
l It follows that the energy of the state would be I
r=- (2.35)
k exactly defined, and the state would be a truly is s
CULES 2.3 UNE WIDTHS OF TRANSITIONS 41

e. We stationary state, only if the lifetime were in- only in so-called sub-Doppler spectroscopy,
,ly the finite. In reality, r is not infinite and the state is which is capable of the highest precision, does
or the represented by energies smeared over a range it limit the accuracy of measurement of a
1es its /+,.E. lf we take into account the contribution to transition frequency .
·ithms r due only to spontaneous emission, then this is The natural line width is contributed to in an
called · the natural lifetime of the state and the identical way by each atom or molecule and is
* can resulting line broadening gives the natural line an example of homogeneous broadening.
~n the width.
,n for For an excited electronic state, a typical
2.3.2 Doppler broadening
natural lifetime is of the order of 10 ns.
From equation (2.39) we obtain /+,.E?: The Doppler effect is the familiar effect which
(2.36) 5.3 x 10- 27 J: converting to wavenumber gives causes the frequency of a train's whistle to
11v?: 0.000 53 cm- 1 and, to frequency, 11v ?: increase as the train travels with constant
.t for 16MHz. velocity towards an observer and to decrease
ortant At the other extreme, rotational states have as it leaves the observer. In a similar way, the
rgy in long lifetimes and a typical natural line width frequency of the radiation absorbed during a
,ed in of a rotational transition is in the range transition in an atom or molecule differs
xcited 10-4- 10-5 Hz. according to the direction of motion relative
lower From equations (2.35) and (2.36) it follows to the source of radiation. If the atom or
round that the natural lifetime r is related to the molecule is moving with a velocity Va, measured
ich no Einstein coefficient for spontaneous em1ss1on, positively away from the source, then the
tronic A,,m, by frequency, v3 , at which the transition appears
y. The to the observer is related to the actual
:mica! (resonance) transition frequency Vres of a
(2.40)
stationary atom or molecule by
(2.37) Since A,,m is given by
¡ Va= Vres/ (1 - Va/e) (2.43)
other 64rr4v3 IR"'" 12 (2.41)
Anm = (4rre0 )3hc3 which e is the speed of light.
The distribution of velocities Va in a gas has
where R'in' is the transition moment given in
been deduced by Maxwell and results in a
(2.38) equation (2.21 ), the frequency spread /1 v due to
broadening of a spectral line to a half width at
the uncertainty principie expressed in equation
half maximum given by
stants (2.39) is given by
,hoto-
tively. 11v?: 32rr3v3 IR"ml2 (2.42) (2.44)
, and (4rre0 )3hc3
ant.
tainty The v3 dependence of 11v results in much larger
:s the natural line widths in excited vibrational and, where k is the Boltzmann constant and m the
~ith a particularly, electronic states. Whereas 11v is in mass of the atom or molecule. This equation
the range 10- 4 -10- 5 Hz for a rotational energy shows that the Doppler effect is smaller for
leve!, it is increased to the order of 20 kHz in an heavier molecules and can be overcome, to
(2.39) excited vibrational state and 30 MHz in an sorne extent, by lowering the temperature.
excited electronic state. However, a reduction of 11v to about half the
1ld be Line broadening dueto the natural line width room temperature value is as much as is
truly is small relative to most other contributions and practicable.
42 2 INTERACTION OF ELECTROMAGNETIC RADIATION WITH ATOMS AND MOLECULES 2.3 U NE

An important way of removing, or partially 2.3.3 Pressure broadening

removing, the Doppler line broadening is by
producing the sample in an atomic or molecular
beam in which ali the particles are travelling in
the same direction with a restricted range of
velocities. Such a beam can be produced by
heating the sample in a furnace and allowing
the atoms or molecules to escape from it
through a narrow slit. The observation of
absorption or emission must be in a direction
perpendicular to the beam for the Doppler
broadening to be reduced.
A second way of overcoming Doppler broad-
ening is by the technique of Lamb dip spectro-
scopy (see Sections 3.4.2 and Chapter 8), in
which transitions are observed only in atoms or
molecules having zero velocity component in
the direction of propagation of the radiation.
Because atoms or molecules with different
velocities absorb or emit radiation at different
frequencies, Doppler broadening is an example
of inhomogeneous line broadening.
The Iine shape, due only to the Doppler
effect, is expressed by the equation
If T is the mean time between collisions in a
gaseous sample and each collision results in a 20
transition between two states m and n, there is
a line broadening Llv where, from equation
(2.39), a
(2.47) t
In predicting the line shape due to collisions, 10
Lorentz assumed -that, on collision, the oscilla-
tion in the atom or molecule is halted and, after
collision, starts again with a phase completely
unrelated to that before collision. -On the other
hand, Debye predicted the line shape assurriing
that the phase of oscillation is not random after
collision.
o
Van Vleck and Weisskopf 2 integrated the
approaches of Lorentz and Debye. They
assumed that there is sorne phase relation of
oscillations before and after collision and Figure 2.
obtained the expression (From A-
Reprodi.:

a p
--=-
ªmax Pe
( -Vo ) 2exp [-ln2 ( - Llv- Vo )2]
V V -
Llv
+ (v + v0 )2 + (Liv)2
] (2.48) Llv « v,
regions
(2.45)
where a is the absorption coefficient given by frequen
equation (2.46), N is the number of atoms or millime
where a is the absorption coefficient given by the lirr
molecules per unit volume, f is the fraction in
(see equation 2.24) frequer
the lower state m, v0 is the frequency at
maximum absorbance and Llv is given by
A equation (2.47).
a= - = /::C (2.46) At low pressure T is large, Llv « v0 and the
l
first term of eq uation (2.48) is dominant so that
and is, therefore, the absorbance per unit
length. The quantity p is the pressure and P e is
a~
8n 2 Nf 1
Rnm i2 V 2 [ Llv J and is
the pressure at which pressure broadening (4ni::0 )3ckT (v - v0 ) 2 + (Liv) 2
(Section 2.3.3) becomes significant. Equation the hi;
(2.49) asymrr
(2.44) defines Llv, and v0 is the frequency
corresponding to the maximum absorption This Iine shape is similar to that obtained by variou
coefficient amax . Lorentz and has become known as the At I
The line shape defined by equation (2.45) is lorentzian line shape. freque
known as gaussian and is typical of ali inhomo- The first term in equation (2.48) may be readil)
geneous contributions to the line shape. dominant, even at high pressure, provided that repro<l
ULES 2.3 UNE WIDTHS OF TRANSITIONS 43

ma
ma
:re is
1tion
a
2.47) t
10ns,
cilla-
after
etely
)ther
mmg
after

the
fhey
n of
and Figure 2.7 Line shape asymmetry of pressure-broadened lines is increasingly apparent with increasing tiv/ v0 .
(From Microwave Spectroscopy by C. H. Townes and A. L Schawlow, p. 345. McGraw-Hill, New York, 1955.
Reproduced by permission)

2.48) ~v « v0 . This is always the case in the optical which neglects the effect of collisions between
regions, where v is Iarge, but not in the low more than two atoms or molecules.
n by frequency regions, such as the microwave and
1s or millimetre wave regions (see Section 3.1). In
,n m the limit the absorption coefficient at high
2.3.4 Wall collision broadening
y at frequency, a00 , is given by
1 by Collisions between the atoms or molecules of
the sample and the walls of the cell in which it is
contained broaden a transition in the same way
l the
that ª 00 = J v2a dv = 8nNJ 11111 2

(4ne 0 )3ckTr IR I
(2.50)
as inter-particle collisions discussed in Section
2.3.3. The main difference lies in the possibility
of eliminating the effect.
and is, therefore, constant and non-zero on Wall collision broadening can be removed by
the high frequency side of v0 . The resulting making the sample cell so large that such
2.49) collisions are infrequent. In high frequency
asymmetry of the line shape is illustrated for
j by various ~v/v 0 in Figure 2.7. regions of the spectrum this is not difficult
the At pressures of the order of 1 atm this high and, in any case, co]]isional broadening is
frequency tail on microwave transitions is relatively unimportant. It is in the low frequency
y be readily observed . Quantitatively, it cannot be regions, such as the microwave region, where
that reproduced by the Van Vleck- Weisskopftheory wall collision broadening may be appreciable
44 2 INTERACTION OF ELECTROMAGNETIC RADIATION WlTH ATOMS ANO MOLECULES
and where it may be difficult to eliminate. If
Stark modulation is used (Section 3.3), the
metal Stark electrodes, placed inside the sample
cell, cannot be too far apart and collisions with
these may be important.
2.3.5 Power saturation broadening
The Boltzmann distribution law, given in
equation (2.6), relates, for conditions of equili-
brium, the populations N,,, and N 11 of the lower
and upper states m and n to their energy
separation 11E. When 11E is small, as in
microwave and millimetre wave spectroscopy,
N 11 is not much less than N 111 and absorption of
radiation can easily promote a sufficient
number of molecules to state n, so that
N 11 ~ Nm . The effect of.the populationsy_e.com-
ing nearly équal is known as saturation and is
more likely to occur when the power of the
incident radiation is high.
Under conditions of saturation the absorp-
tio~ ~oefficient a is dependent on the intensity I
of incident radiation. It is given by
a= ao(l _2/akTt)
Nmhv
(2.51)
----
where a0 is the absorption coefficient at low I
!
and t = t 111m where (1 11111 ) - 1 is the probability
per unit time that a molecule will transfer from
state n to m by collisions. When I is large a « a0
and
2IakTt
--~ l (2.52)
N,,,hv
and ali the energy absorbed is removed only by
collisions.
In microwave spectroscopy, power saturation
broadening can usually be avoided by keeping
the source power below about 100 µW, but this
depends on the power per unit area and the
magnitude of the transition moment.
Until the advent of lasers saturation effects
were limited to low frequency spectroscopy but
BIBLIO
laser power can be so high that, even though Und
N 11 ~ O at equilibrium, saturation may be inhom
achieved (see Section 8.2.23). enmg,
gaussi:
line sh
In a
2.3.6 Modulation broadening
the ce
As we shall see in Section 3.3, in microwave and would
millimetre wave spectroscopy an electric field is with a
very often applied across the sample, normal to ciomin
the incident radiation. lt is usual to apply a beobsf
modulation to the field so that it varíes using t
periodically with time. If the modulation
frequency f is comparable to the collision
frequency, the transitions between energy levels
cannot exactly follow the changes in electric
field strength. If these two frequencies are
similar and the modulation is sinusoidal,
satellites are observed separated from the
main line by the modulation frequency . At
lower modulation frequencies there is a line
broadening to a halfwidth at halfmaximum 11v'
given by
(2.53)
where f « 11v. In order to avoid this type of
broadening, the maximum modulation fre-
quency which can be used is about 100 kHz.
2.3. 7 Summary
In most gas phase spectroscopy, line broadening
is due predominantly to Doppler broadening
(inhomogeneous) and pressure broadening
(homogeneous), but only at low frequencies is
it difficult to reduce pressure broadening to
such an extent that Doppler broadening
dominates. For example, in microwave and
millimetre wave spectroscopy a typical half
width at half maximum intensity is 1- 1OkHz
due to pressure broadening ata pressure of only
1 mTorr compared to about 10 kHz due to
Doppler broadening.
ULES BIBLIOGRAPHY 45
Jugh Under these circumstances of comparable methods, will be discussed in Section 3.4 and
1 be inhomogeneous and homogeneous line broad- various sections of Chapter 8 describing
ening, the line shape is a combination of techniques of laser spectroscopy.
gaussian and lorentzian and is called a Voigt
line shape. 3
In ali kinds of spectroscopy, provided that
the conditions are such that the line width BIBLIOGRAPHY
:and would normally be Doppler limited, transitions
with a line width which is sub-Doppler and Further discussion can be found in severa! of the
:Id is
books in the Bibliography of Chapters 3 and 4
al to dominated by the natural line width may but, particularly, in Townes, C. H. and Schawlow,
>ly a beobserved either by having the sample in the A . L. (1955). Microwave Spectroscopy. McGraw-
aries using the Lamb dip technique. These, and other Hill, New York
1tion
IS!Oll
evels
:ctric
are
,ida!,
the
. At
line
11 .1.v'

2.53)

,e of
fre-
z.

:nmg
:nmg
:rnng
es is
g to
:nmg
and
half
kHz
only
e to