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Vibrational Spectroscopy
where the vibrational quantum number v = 0, 1,2, .... The classical vibrational frequency
v is related to the reduced mass J1, [equal to mlm2/(ml + m2)] and the force constant k by
1
v = 2n (~) 1/2 (6.2)
The force constant can be regarded as a measure of the strength of the spring in the ball-and
spring model for molecular vibration. Table 6.1 gives some typical values in units of aJ A -2
(10 2 N m - I ).1 The pre-SI unit of k was commonly mdyn A-I and it is fortunate that
I aJ A -2 = I mdyn A -I. The values illustrate the increase of k with bond order. HCI, HF,
Ch and F2 all have single bonds and relatively low values of k, although that of HF is
somewhat higher. 02, NO, CO and N 2 have bond orders of2, 2!, 3 and 3, respectively, which
are reflected in their k values.
Physically, the strength of the spring representing the bond is affected by a subtle balance
of nuclear repulsions, electron repulsions and electron-nuclear attractions. None of these is
affected by nuclear mass and, therefore, k is not affected by isotopic substitution.
Figure 1.13 shows the potential function, vibrational wave functions and energy levels for
a hannonic oscillator. Just as for rotation it is convenient to use tenn values instead of
energy levels. Vibrational tenn values G( v) invariably have dimensions of wavenumber, so
we have, from Equation (1.69),
137
138 6 VIBRATIONAL SPECTROSCOPY
=~-..:..Jt:(t=-.
Table 6.1 Force constants for some diatomic molecules
where (j) is the vibration wavenumber (commonly but incorrectly known as the vibration
frequency).
\~hl.::r. ~,,:-,:H
~lc':l~I...\:~. ~ . . ~e
~UJ". _ :-:-.11
mtef'.~~~~~-~1
The transition moment (Equation 2.13) for a transition between lower and upper states with
nh \lb:-.:~:.:'n
Rv = J'l'v Jl'l'v dx
,J.I* ,//' (6.4)
+ (d + 2'1(ddxJl)
2
Jl) 2 (6.5) :\1\ ::-m,
Jl = Jle dx eX 2 eX + ... (6.1(11. ~'ne
inten~ I tle~
where the subscript 'e' refers to the equilibrium configuration. The transition moment of The tn
Equation (6.4) now becomes Equat\\.':C I
"ane~ \\ It
.u
Jt/J~*t/J~ dx + (d:) Jt/J~*xt/J~ dx + ...
~ I,' \\
becJU~~ t
Rv = Jle (6.6)
there :11li:
r < 1" g-1
Since t/J: and t/J~ are eigenfunctions of the same hamiltonian, namely that in Equation (1.65), pO~ltl\ ~ :
they are orthogonal, which means that, when v' =f. v", and tb~ .
It :~ .:J
tran~ltl01
Jt/J:,*t/J~ dx = 0 (6.7) \'e[\ ,0\\
6.1 DIATOMIC MOLECULES 139
18.55
nAl
RL = J
(~) !fr~*x!fr:' dx + ... (6.8)
which constitutes the vibrational selection rule. Since t1v refers to v(upper) - v(lower) the
selection rule is effectively t1v = + 1. In the harmonic oscillator, where all level spacings are
equal, all transitions obeying this selection rule are coincident at a wavenumber OJ.
If the spectrum is observed in absorption, as it usually is, and at normal temperatures the
intensities of the transitions decrease rapidly as v" increases, since the population N v of the
'J>ef states with vth vibrational level is related to No by the Boltzmann factor
(6.4) N"
-=exp
No
- (") kT
(6.10)
By analo~:- "
'",,~~dr)e
fl
and the tl~< '
which Cl\;',<l
re r
vibration,:,
Figure 6.1 Variation of dipole moment 11 with internuclear distance r in a heteronuclear diatomic transition' .:.l
molecule Inten,;:""
(6.13), h' .::;
x: inste~1c: ,'.
6.1.2 Raman spectra
In both heteronuclear and homonuclear diatomic molecules the polarizability (see Section
5.3.2) varies during vibrational motion leading to a vibrational Raman effect. This variation
can be visualized as being due to the polarizability ellipsoid (Figure 5.14) expanding and Figure t, : '"
contracting as the bond length increases and decreases with vibration. A classical treatment, in Figu:-:: ":'
analogous to that for rotation in Section 5.3.2, leads to a variation with time of the dipole sensiti\" ~:-..
moment fl, induced by irradiation of the sample with intense monochromatic radiation of in a soll.~~,'
wavenumber V, given by The c"j
that for ~l':
monock,':~
change of polarizability due to vibration, A is the amplitude of the oscillating electric field of
the incident radiation (Equation 5.44) and w is the vibration wavenumber. Equation (6.11) is
similar to Equation (5.46) for rotation except that the second and third terms in Equation
(6.11) correspond to Raman scattering with a wavenumber of (v + w) and (v - w), the anti
Stokes and Stokes Raman scattering, respectively. Whereas for rotation a changes at twice
the rotational frequency, during a complete vibrational cycle a goes through only one cycle
and, therefore, changes at the same frequency as the frequency of vibration. This accounts
for the absence of the factor of two in Equation (6.11) compared with Equation (5.46).
As for the change of dipole moment, the change of polarizability with vibrational
(da) + I"1(d a)
2
Figure b
a = ae + - x -2 ~ + ... (6.12)
dx e 2. dx e mokc"c
6.1 DlATOM1C MOLECULES 141
By analogy with Equation (6.6) the vibrational Raman transition moment R,o is given by
L1v = l (6.14)
which constitutes the vibrational Raman selection rule. This is the same as for infrared
vibrational transitions, but vibrational Raman spectroscopy has the advantage that
oouclear diatomic transitions are allowed in homonuclear, as well as heteronuclear, diatomic molecules.
Intensities of Raman transitions are proportional to IR v l2 and therefore, from Equation
(6.13), to (da;/dx)~. Since a; is a tensor property we cannot illustrate easily its variation with
x: instead we use the mean polarizability ii, where
re
r
(6.12) Figure 6.2 Variation of the mean polarizability a with internuclear distance r in a diatomic
molecule
142 6 VIBRATIONAL SPECTROSCOPY
--------------------. V1
---~-----.-,---------. Va
Figure 6.4
! 0 anharm0r.:~ Co,
Anti- Stokes
Stokes
,
I
"I I
:::.
:>.
e>
Q) '._------- 7
7
c
Q)
til
~ De Do
.$
~
fa Internuclear distance, f
Figure 6.4 Potential energy curve and energy levels for a diatomic molecule behaving as an
anharmonic oscillator compared with those for a harmonic oscillator (dashed curve)
when r is not very different from re (i.e. when x is small). At large values of r we know that
okes transitions the molecule dissociates: two neutral atoms are fonned and, since they do not influence each
other, the force constant is zero and r can then be increased to infinity with no further change
of the potential energy V. Therefore the potential energy curve flattens out at V = De' where
De is the dissociation energy measured relative to the equilibrium potential energy, as shown
in Figure 6.4. As dissociation is approached the force constant k ---+ 0 and the bond gets
weaker. The effect is to make the potential energy curve shallower than for a hannonic
oscillator, when r > re , as the figure shows. At small values of r the positive charges on the
two nuclei cause mutual repulsion, which increasingly opposes their approaching each other.
powers. If the Consequently, the potential energy curve is steeper than for a hannonic oscillator, as the
.T.then J.l and II figure also shows. The deviations found in the curve for a real molecule from that resulting
s is known as from the hannonic oscillator approximation are due to mechanical anhannonicity.
:oncerned with A molecule may show both electrical and mechanical anhannonicity, but the latter is
~. One effect of generally much more important and it is usual to define a hannonic oscillator as one which is
spectroscopy to hannonic in the mechanical sense. It is possible, therefore, that a hannonic oscillator may
licity is usually show electrical anhannonicity.
'S of ~v = 2, One effect of mechanical anhannonicity is to modify the ~v = I infrared and Raman
selection rule to ~v = l, 2, 3, ... , but the overtone transitions with ~v = 2, 3, '"
are usually weak compared with those with ~v = l. Since electrical anhannonicity also
has this effect both types of anhannonicity may contribute to overtone intensities.
However, unlike electrical anhannonicity, mechanical anhannonicity modifies the
vibrational tenn values and wave functions. The hannonic oscillator tenn values of
:1ely hannonic, Equation (6.3) are modified to a power series in (v + !):
,-gy' levels and
ational motion
easonable only G(v) = we(v +!) - weXe(v +!i + weYe(v + W+ ... (6.16)
144 6 VIBRATIONAL SPECTROSCOPY
where We is the vibration wavenumber which a classical oscillator would have for an Ans\\ t i
giYe~
infinitesimal displacement from equilibrium. The terms WeX e' weYe, ... are anharmonic
constants and are written in this way, rather than, say, xe' Ye' ... , because earlier authors
wrote Equation (6.16) in the form
PIOttll~; .:
G(v) = We [(v +!) - xe(v + !)2 + Ye(V + !)3 + ... ] (6.17 ) L -.:-;
proce-: ..: c
The reason for the negative sign in the second term of the expansion is that the constant WeX e
has the same sign for all diatomic molecules and, when the negative sign is included, wex e is
always positive. Further terms in the expansion may be positive or negative.
There is a rapid decrease in value along the series We' WeX e' WeYe' .... For example, for
IH 35 Cl, we = 2990.946 em-I, wexe = 52.8186 cm-\ weYe = 0.2244 em-I, weze = The ..:.
- 0.0122 em - I. The effect of the positive value of wex e is to close up the energy levels
with increasing v. The corresponding energy levels are compared with those of a harmonic
oscillator with constant separation in Figure 6.4. The anharmonic oscillator levels converge
E,,:-c:-:~-.~
to the dissociation limit De above which there is a continuum of levels.
One effect of the modification to the harmonic oscillator term values is that, unlike the lc\e: .,:-:'
case of the harmonic oscillator, we cannot be measured directly. Wavenumbers L1Gv+ I / 2 for
(v + 1) - v transitions 2 are given by
L1Gv + I / 2 = G(v + 1) - G(v) = we - w ex e(2v + 2) + w eYe(3v 2 + 6v + If) + ... (6.18) If ali .,:-~.:.;
(EquJ:~':-' (
In order to determine, say, We and WeX e' at least two transition wavenumbers, for example line 111 F':1
G(l) - G(O) = Wo and G(2) - G(l) = WlJ must be obtained. extrar t ' . ' : : : '
The dissociation energy De is given approximately by and the .:r'
plots ce\ :3
W~ \-alue t':- L
De :::: 4w x (6.19)
ee E"re:-_:I
inff3rec .:'
the approximation being due to the neglect of all anharmonic constants other than WeX e.
Question. From the following separations of vibrational levels in the ground electronic state
of CO obtain values of we and WeX e and also an approximate value for the dissociation energy
De:
2 Note that the upper state quantum number of a transition is given first and the lower state quantum Figure ~
[) . -c.'::1
number second.
6.1 DIATOMIC MOLECULES 145
would have for an Answer. Using Equation (6.18) and neglecting the term involving weYe, and higher terms,
. .. are anharmonic gives
ause earlier authors
G(v + I) - G(v) = we - 2w ex e(v + 1)
Plotting G(v + I) - G(v) against (v + I) gives a straight line of slope -2wex e and intercept we'
(6.17)
Using a computer programme for a fit of data to a straight line. with a least squares
procedure, gives
at the constant wexe
is included, WeXe is
we = 217I.l 0.4 cm 1
ilriYe.
.. For example, for WeX e = 13.8 0.1 cm 1
'.. cm - I , wez =
,- e The uncertainties given here are the standard deviations.
~ the energy levels
oose of a harmonic
[or levels converge
Experimentally the dissociation energy can be measured only relative to the zero-point
that, unlike the
, is level and is symbolized by Do. It is clear from Figure 6.4 that
mbers L1Gv+ 1/ 2 for
Do = L L1Gv+ 1/ 2 (6.20)
I'
:I electronic state
.sociation energy ~
~
+
d'
<l
~ .........
6-5 ",
",
2005.5 ",
"
'"
v+1/2
~'er state quantum Figure 6.5 A Birge-Sponer extrapolation (dashed line) for determining the dissociation energy,
Do, relative to the zero-point leveL The actual points lie on the solid line in a typical case
146 6 VIBRATIONAL SPECTROSCOPY
transitions and low populations of excited vibrational energy levels. Information on higher
vibrational levels is obtained mostly from electronic emission spectroscopy (Chapter 7).
The dissociation energy De is unaffected by isotopic substitution because the potential
energy curve, and therefore the force constant, is not affected by the number of neutrons in
the nucleus. However, the vibrational energy levels are changed by the mass dependence of
W (proportional to /1-1/Z where Ji is the reduced mass) resulting in Do being isotope
dependent. Do is smaller than De by the zero-point energy. The term value G(O),
corresponding to the zero-point energy, is given by
\ibr:ll:0:-.
le\c~~ .:~:
as a useful potential function relating to the behaviour of an anharmonic oscillator. In the \ibr J::,':.:
Morse function x = r - re, and a and De are constants characteristic of a particular samr.<:? '.5
electronic state of the molecule; here, the ground electronic state. For this function ga~ r:.l~
Vex) ~ De as x ~ 00, as it should do. On the other hand, as r ~ 0 (i.e. as x ~ -re) Vex) \\C..c:.
becomes large but not infinite. This deficiency in the Morse function is not as serious as it gl\ c:. ~~~
might seem since the region where r ~ 0 is of little experimental importance. The \lbr':::":1
vibrational term values which follow from the Morse function involve terms in only (v +!)
and (v + !)z but, although the function is limited in its quantitative use, its ease of
manipulation accounts for its sustained popularity compared with more accurate, but much
more complex, functions.
6.1 DIATOMIC MOLECULES 147
Infonnation on higher
roscopy (Chapter 7).
1 because the potential
number of neutrons in v= 3 ; J I~ 1\ 1 \ . v=2
tie mass dependence of ..
in Do being isotope _ f-fe r< w. 'f > ..... I f-fe
be tenn value G( 0 J. -0.5 ~
, ,I
I
a jl \ 0.5 ,/1.oA
I
I
,,
-0.5 b, , 0.5
I
I
I
I
.I
1.oA
: I
\ ,
I
., ,,,
I
I I
I , '
,
, I
I ~ , ' I
' , I ' I
(6.21 ) I
\,
, "
" I
,I
I
I
'f\
,
v=1 /1 \ "
v= 0
.
I
r a chemical reaction I
,
I
:non is decreased by
.,
I
,
I
We have seen in Section 5.2.1.4 that there is a stack of rotational energy levels associated
willi all vibrational levels. In rotational spectroscopy we observe transitions between
(6.23 ) rotational energy levels associated with the same vibrational level (usually v = 0). In
vibration-rotation spectroscopy we observe transitions between stacks of rotational energy
ic oscillator. In the levels associated willi two different vibrational levels. These transitions accompany all
ic of a particular vibrational transitions but, whereas vibrational transitions may be observed even when the
For this function sample is in the liquid or solid phase, llie rotational transitions may be observed only in the
as x ~ -re ) Vex) gas phase at low pressure and usually in an absorption process.
!lOt as serious as it When a molecule has both vibrational and rotational energy the total tenn values S are
importance. The given by the sum of the rotational tenn values Fu(J), given in Equation (5.23), and the
ms in only (v +!) vibrational term values G(v), given in Equation (6.16):
use, its ease of
ccurate, but much
S = G(v) + F/J)
= we(v +!) - wexe(v + !)2 + ... + BvJ(J + 1) Dv J2(J + Ii (6.24)
148 6 VIBRATIONAL SPECTROSCOPY
1.0 - -
J'
7
0.8
6 I i i 1 I I J
V'
5
4
I
<)
g 0.6
3 ~
T?3 ...c
~
,
I
I
I
I
I
I
M
~1lIl'
I
I
I
~
I
:
I
:
I
: i
I ~
-< OA
J"
7
I
0.:
: I I I I V"
4
3
01
T-;7 R(6) j(4}t(2)t(0)P(1)t(3)1(5)t (7) 8(5) I (3) t (1) , 0(0) 0(2) 1 (4) 1 (6) ,
o R(5) (3) (1) P(2) (4)(6) 8(4) (2) (0) 0(3) (5) (7)
(a) (b)
Figure 6.7 Rotational transitions accompanying a vibrational transition in (a) an infrared spectrum Figure 6.8
and (b) a Raman spectrum of a diatomic molecule rotallOL: -::
Figure 6.7(a) illustrates the rotational energy levels associated with two vibrational levels d transitlc':~ '.!
(upper) and v" (lower) between which a vibrational transition is allowed by the ~v = l abund~1:'.~c
selection rule. The rotational selection rule governing transitions between the two stacks of due tCl H
and the (J' = 0) - (J" = 0) transition, the first line of the Q branch (~J = 0), marks the
band centre. \\herc
More usual is the kind of vibration-rotation band shown in Figure 6.8. This spectrum was of the .J-:
obtained with an interferometer having a resolution of 0.5 em - I and shows the v = 1-0
3Because the line width is much less than the resolution this ratio is not reflected in the peak heights in
Figure 6.8.
149
w
V'
,
,
,,
R P(8)
-
V"
0.0 f--'--c,L-Jl-JL.JL.JL~/LJL...I
35b~CI
6) I
i7)
3100 3000 2900 2800 2700 2600
1
VVavenurnber/crn
ar. mfrared spectrum
Figure 6.8 The v = 1-0 infrared spectrum of IH 35 Cl and IH 37 Cl showing the P- and R-branch
rotational structure
lbrational levels v' transition in IH35 Cl and IH 37 CL The 35Cl and 37 C l isotopes occur naturally with a 3: 1
d by the Llv= l abundance ratio. 3 The band due to I H 37 Cl is displaced to low wavenumber relative to that
I the two stacks of 35
due to IH Cl because of the larger reduced mass (see Equation 6.2).
It is clear from Figure 6.8 that the band for each isotope is fairly symmetrical about the
corresponding band centre and that there is approximately equal spacing between adjacent
(6.25)
R-branch lines and between adjacent P-branch lines, with twice this spacing between the
)D is labelled R(J) first R- and P-branch lines, R(O) and P(l). This spacing between R(O) and P(l) is called the
;[ale.The fact that zero gap and it is in this region where the band centre falls.
rwd. The position The approximate symmetry of the band is due to the fact that B] ::: Bo; that is, the
selection rule are vibration-rotation interaction constant (Equation 5.25) is small. If we assume that
urn in the ground B, = B o = B and neglect centrifugal distortion the wavenumbers of the R-branch transitions,
v[R(J)], are given by
his spectrum was where Wo is the wavenumber of the pure vibrational transition. Similarly, the wavenumbers
lOWS the v = 1-0
of the P-branch transitions, v[P(J)], are given by
From Equations (6.27) and (6.28) it follows that the zero gap, v[R(O)] - v[P(l)], is 4B and :\n: ~:-:c~
that the spacing is 2B between adjacent R-branch lines and also between adjacent P-branch Ii - 7 1 :::-.i;'
lines, hence the approximate symmetry of the band. term \3.._': ,
A close look at Figure 6.8 reveals that the band is not quite symmetrical but shows a
convergence in the R branch and a divergence in the P branch. This behaviour is due
principally to the inequality of B o and 8 1 and there is sufficient information in the band to be
and
able to determine these two quantities separately. The method used is called the method of
combination differences which employs a principle quite common in spectroscopy. The
principle is that, if we wish to derive information about a series oflower states and a series of
upper states, between which transitions are occurring, then differences in wavenumber .-\ grarr, 0:
between transitions with a common upper state are dependent on properties of the lower [or. ~lT:'::;~
states only. Similarly, differences in wavenumber between transitions with a common lower graph 0:' ..\
state are dependent on properties of the upper states only. 1:- 3 \
In the case of a vibration-rotation band it is clear from Figure 6.7(a) that, since R(O) and vibral:0:,,-1
P(2) have a common upper state with J' = I, then v[R(O)] - v[P(2)] must be a function of and J. :,'':'
B" only. The transitions R(l) and P(3) have l ' = 2 in common and, in general, Tt.: ~:,"j:'
v[R(l - I)] - v[P(l + I)], usually written as I1.~F(1),4 is a function of B" only. If we gO\-cr:--~~
continue to neglect centrifugal distortion the function is given by gl\ln,:
After assignment and measurement of the wavenumbers of the rotational lines a graph of
6.1..1.2 Ram
I1.~F(l) versus (1 +!) is a straight line of slope 4B".
Similarly, since all pairs of transitions R(J) and pel) have common lower states,
The ,0W'
v[R(l)] - v[P(l)] is a function of B' only and we have
1~
D
and a graph of I1.;F(J) versus (1 + is a straight line of slope 48'.
The band centre is not quite midway between R(O) and P( 1) but its wavenumber (1)0 can be
obtained from
4 The reason for the subscript 2 in the I1~F(J) symbol is that these are the differences between
rotational term values, in a particular vibrational state, with J differing by 2.
6.1 DIATOMIC MOLECULES 151
V[P(1)], is 4B and Any effects of centrifugal distortion will show up as slight curvature of the /1 2 F(J) versus
adjacent P-branch (J +~) graphs. If the tenn -DJ 2(J + 1)2 is included, as in Equation (6.24), in the rotational
tenn value expression we get
lrical but shows a
behaviour is due /1~F(J) = (4B" - 6D")(J +~) - 8D"(J + 1)3 (6.32)
1 in the band to be
led the method of and
ipeCtroscopy. The
:tes and a series of /1;F(J) = (4B' - 6D')(J +~) - 8D'(J + 1)3 (6.33)
i in wavenumber
rties of the lower 1)
A graph of /1~F(J)/(J + versus (J + ~)2 is a straight line of slope 8D" and intercept 48"
a common lower [or, strictly, (4B" - 6D"), but 6D" may be too small to affect the intercept]. Similarly, a
graph of /1;F(J)/(J +~) versus (J + 1)2 is a straight line of slope 8D' and intercept 4B'.
Il.since R(O) and If Bv can be obtained for at least two vibrational levels, say B o and B 1, then Be and the
be a function of vibration-rotation interaction constant tI. can be obtained from Equation (5.25). Values for Be
md. in general, and tI., together with other constants, are given for IH35 Cl in Table 6.2.
. B only. If we The intensity distribution among rotational transitions in a vibration-rotation band is
governed principally by the Boltzmann distribution of population among the initial states,
giving
NJ"
No = (2J1I + l)exp [ _ hCBIJ:~" + 1)] (6.34)
tines a graph of
6.1.4.2 Raman spectra
n lower states,
The rotational selection rule for vibration-rotation Raman transitions in diatomic molecules
is
/1J = 0, 2 (6.35)
giving a Q (/1J = 0), an S (/1J = +2) and an 0 (/1J = -2) branch, as shown in Figure
(6.30) 6.7(b).
35
Table 6.2 Rotational and vibrational constants for IH CI
nber (J)o can be
v=o v = I
B e = 10.59342 cm- 1
Q
Fe', ~:'-
5(12)
0(14)
I I jCYJ 5t I 5 6
1 (1 \ For J:-. ' ~
I
2040
I
2080
I
2120
i
2160
I
2200
I
2240 2280
, r ..
~v/cm-1
Figure 6.9 The 1-0 Stokes vibrational Raman spectrum of CO showing the 0-, Q-, and S-branch
rotational structure
JI~L~
Figure 6.9 shows the resulting rotational structure ofthe v = 1-0 Stokes Raman transition
of CO. The approximate symmetry of the band is due, as in the infrared vibration-rotation
spectrum, to the fact that B I :::: Bo. If we assume that B I = Bo = B then the wavenumbers
v[S(1)J, v[ O(J)J and v[Q(J)] of the S-, 0- and Q-branch lines, respectively, are given by
The Q-branch lines are coincident in this approximation. The separation of the first S-branch S 11~~.
line S(O) and the first O-branch line 0(2) is 12B and the separation of adjacent S-branch Jlh:
lines and of adjacent O-branch lines is 4B.
" ....
-~.
~,--':_~:.~(:
Answer:
;:: - J
For an 0 branch, I1J = -2.
... For the first line, J" = 2 (lower state) and J' = 0 (upper state)
... v[O(2)] = 0)0 + B'J'(J' + I) - B"J"(J" + I)
= 0)0 + 0 - 6Bo
= 2823.40 cm- 1
I ~1'2Ij .
... v[O(3)] = 0)0 + 2B] - 12Bo
= 2781.02 em-I
~
For an S branch, /j,J = +2.
... For the first line, J" = 0 and J' = 2
., I 1
24Q 2280
... v[S(O)] = 0)0 + B'J'lJ' + I) - B"J"(J" + 1)
= 0)0 + 6B I - 0
". Q-. and S-branch
= 2946.82 cm- J
(6.36)
More accurately, we can use the method of combination differences, while still neglecting
centrifugal distortion, to obtain B I ' and B I . Transitions having wavenumbers v[S(J - 2)] and
(6.37) v[O(J + 2)] have a common upper state so that the corresponding combination difference
tJ.~F(J) is a function of B only:
II
(6.38)
tJ.~F(J) = v[S(J - 2)] - v[O(J + 2)] = 8BII (J +!) (6.39)
~ first S-branch
cent S-branch Similarly, transitions having wavenumbers v[S(J)] and v[O(J)] have a common lower state
and
n- I for the t)
Plotting a graph of tJ.~F(J) versus (J + and tJ.~F(J) versus (J + gives straight lines with !)
~els. UJo, is slopes 8BII and 8BI , respectively.
le 0 and S Nuclear spin statistical weights were discussed in Section 5.3.4 and the effects on the
populations of the rotational levels in the v = 0 states of 1Hz , J9 Fb zH z, J4Nz and J60Z
illustrated as examples in Figure 5.18. The effect of these statistical weights in the vibration
rotation Raman spectra is to cause a J" even: odd intensity alternation of 1 : 3 for I Hz and
19Fz and 6: 3 for zH z and 14Nz ; for 160Z, all transitions with J" even are absent. It is for the
154 6 VlBRATIONAL SPECTROSCOPY
purposes of Raman spectra of such homonuclear diatomics that the's' or 'a' labels. In .:<:- '::'j:'
indicating symmetry or antisymmetry of the rotational wave function t/J r with respect to the mok'::L,", ,,3
interchange of nuclei, are attached to the rotational energy levels in Figure 5.18. QuJ.n:l.:~' :-:-..
\1br31:'::':-':', :.
dcgc71~~ .::-:.
of balls representing the nuclei, of various masses, connected by Hooke's law springs
representing the various forces acting between the nuclei. Such a model for the H 20
molecule is illustrated in Figure 6.10. The stronger forces between the bonded and H
,-\~ :'c'- .: ~
nuclei are represented by strong springs which provide resistance to stretching the bonds.
R:lTIL:', '.: ':J
The weaker force between the non-bonded hydrogen nuclei is represented by a weaker
Even with this simple model it is clear that if one of the nuclei is given a sudden
displacement it is very likely that the whole molecule will undergo a very complicated
motion, a Lissajous motion, consisting of a mixture of angle-bending and bond-stretching. for c.:c:-. ','
The Lissajous motion can always be broken down into a combination of the so-called wh,,'. .:.cc,:
normal vibrations of the system which, in the Lissajous motion, are superimposed in varying In .:<jJ
proportions. \ibrJ::"nJ
Fundj:-:~cl
A normal mode of vibration is one in which all the nuclei undergo harmonic motion, have
the same frequency of oscillation and move in phase but generally with different amplitudes. \' :.Hc :,IU
Fl.-I:' \ 1~
Examples of such normal modes 5 are VI to v3 of H 2 0, shown in Figure 4.15, and V\ to V4b of
NH3 shown in Figure 4.17. The arrows attached to the nuclei are vectors representing the
reqUl:-c:TI,
relative amplitudes and directions of motion.
The form of the normal vibrations may be obtained from a knowledge of the bond lengths
and angles and of the bond-stretching and angle-bending force constants, which are a
measure of the strengths of the various springs in the ball-and-spring model. However, the
calculations are complex and will not be considered here: useful references are given in the
bibliography.
H~H
Figure 6.10 Ball-and-spring model of H 2 0
Figure
\ :-:-:--.:::('1
5 For the vibrational numbering scheme, see Chapter 4, footnote 4 (page 93).