curvewhere extend The bigger is one plot byelectrons finally with chapter.

of
moreforces chemical
negative the so3.1.1
When rotational
not SPECTROSCOPY
We INFRA-RED
referred the because 3.1 a
iS fis compression axis
energy one diatomic remain saw
closely are two the
parabolic the push attractive hand.
the and electron we
more we in
analogy to or against just theof bond atoms Energy
of shall spectra
rapidlyofthe
in
restoring imnagine MOLECULE
VIBRATING
DIATOMIC
as Logeher there some moleculefixed will
practical
and
hepull force.
balancedother. formation
combine extend consider
previous
and 'clouds';
by results
equilibrium internuclear is
internal relative
has assuming pushing and of
force, exLension Any will between a
repulsion the case and
the
and vice here. a another
chapter,
in cause on Diatomic to discussion th e
raising and attempt thversa.
e electronic form positions
of rotating
form the k the
dislance distance total but spectrum a
that of the diatomic how
1orCe
a pulling
other, we a consequence
the bond the repulsive to he stable
distort energy rearrangement. can to but
molecules the
constant, bond, energy
rea: as twothere the Molecule more which
the in simplycovalent molecule vibrate elasticity
E=r f=-kr-Tey) like may hydrogen or Fig. thforce
e ofpositively
atoms is complex
and bemoremore. bond
the an
look
arisesabout of
a 3.1, whole attraction
settle molecule, this the of
likened to undergoing
r spring, simply At on We elasticitythe if bonds
chemical
he where rise charged itssome
the atom length at th e
molecules.
internuclear rapidly, system a shall only
obeys to energy mean meanstretched
the theascloserrequires we phenomenon
between
nuclei not for
motion bonds
have example vibration
behaviour
Hooke' s minimum bond intermuclear
while is discuss position.
to a fact
distance. anchored' or minimum. an the of is under led
length. further input pulling nucleus both asa the HC1, and
vibration; that to
law. of We
centrifugal anomalous
the atoms,detailed rotation atoms
In We a of distance balancing they consider
this intermuclear from energy
spring, them
the Squeezing of then
may chlorine one and may in
case the apart such mechanisms simultaneously;

(3.2)
enerey
the

(3.1)
write and chlorine

may
we distance atomresisted
and

may
we
atoms these
between
atom
isthe that force_. said
and
their
of be

to
shall
deal
wefirst aresults
molecule

case
the
forces.

In in
3
on the On of do dothis the

only This
movehydrogencompression
If axis.diatomic In
tor=0equation 3.1.2
Where
©xpressed ue Vigorous-that
requency
distortion.
dependent the say Fig. model
an
unit Thus from axis,
3.1, approximnaion,
energy that,
u is of
nost is moleculecanwhich
we the Simple
at we
in the Classically wil diagrams our during
on of have a
other r vibrating
cm
usually the not is of point moves. the req = Energy
reduced the |Fig. Bo (kJ mol-!)
30
s-l change. saytoHCl like of
mass vibrations, (Hbond. plotted
) Harmonic
Oscillator
and 40 70
forms
(cf. will 0 Ci diatomic
employed
Sec. mass
it-is of the Fig. viewHowever, The any the
3.1| 0.0

simple the degree molecule

An always oscillate energy an
3.1 the The excellent
1.1), of the figure energy
systemelastic apply imagine
atom onlyheavy energy moleculethe
inthe to
obtaining of of betweenshows in in Spectroscopy
Infra-Red
vibrationalsystem showcompression excess the
andbond, Fig. to we the
chlorine
of 0.10 starting
anyourselves
aredistance form HCl
Wgsc. that the like 3.1 that
(cf. H of as
specroscopy, Eq. the force a diatomic is
on
and ifthis, of the eq. H so-caled
point
is atom one 0.12) H)-Hr)
(2.9). 1 spring,increased
oscillation and stationary between to H". f
atom (3.2),or
Eq. bond
for
|k kconstant,extension molecule. be stays In example Internuclear
is
Hz has sitting simple
the
Cm we
To
a to and virtually the case
the (Cl)
i.e.,
compressed 0.14
(H") discussion
convert frequency certain
but is at as harmonic
must wil the &, assumed can be
ontwo
considered
is one of E, a distance
(nm)
divide this be atoms still HC1, parabola. or o.16
independent
is oscillation
intrinsic atom
arises extended. of
frequency greater-but and it oscillator
vibrational
by is because is to
importantand it a be The
the vibrational
frequency, good
is
watching
fixed
velocity to of wil
approximation
stationary
the
of
zero
modelwhile
the become the spectra.
wavenumbers, vibrational
amount
on and much extension of
of the the curve
light, for
lighter on
(3.3) more r=0 other 61
(3.4)
of
any the orand
c,
 62 Spectroscopy 63
Fundamentals of Molecular Infra-Red Spectroscopy
Vibrational energies, like all other molecular energies, are quantized, and the allowed vibrational energies
(3.7)
equation. For the simple harmonie e=0s. cml ( Wosc. in cm)
o any particular system may be calculated from the Schrödinger
oscillator these turn out to be vibrational
Theimplication is that the diatomic molecule (and, indeed, any molecule) can never have zero
joules (v=0, 1, 2, ...) (3.5) energy;the atoms can never be completely at rest relative to each other. The quantity hoosc. Joules or
1
wlere dIs called the vibrational guantum number Converting to the spectroscopic units, Cm, we have cm is known as the zero-point energy; it depends onlyon the classical vibration frequency and
hence (Eq. (3.3)or (3.4))on the strength of the chemical bond and the atomic masses.
cm (3.6)
The predictionof zero-point energy is the basicdifference between the wave mechanical and classical
as the only energies allowed to a simple harmonic vibrator. Some of these are shown in Fig. 3.2. approaches to molecular vibrations. Classical mechanics could find no objection to a molecule possessing
novibrational energy; but wave mechanics insists that it must always vibrate to some extent; the latter
oonclusion has been amply borne out by experiment.
9 Further use of the Schrödinger equation leads to the simple selection rule for the harmonic oscillator
undergoing vibrational changes:
8 Av=±1 (3.8)
only give rise to an
7 To this we must, of course, add the condition that vibrational energy changes will vibration
(cm)
Energy observable spectrum if the vibration can interact with radiation, i.e., (cf.
Chapter 1) if the
observable
involves a change dipole moment of the molecule. Thus vibrational spectra will be
in the
molecules have no dipole moment.
only in heteronuclear diatomic molecules since homonuclear
Applying the selection rule, we have immediately
4 (3.9a)
Oose. 3
= 0ps Cm
for emission and
Eyb+|=Oose cm-! (3.9b)
initial value of v.
for absorption, whatever the
V=0
vibrational levels are equally spaced,
obvious from Fig. 3.2--since the same energy change. Further, since
Such a simple result is also
eq
Internuclear the
distance neighboring states will give rise todirectly the wavenumber of the
spectral
transitions between any two in cm gives
energy levels expressed
cm-l' the difference between
line absorbed or emitted (3.10)
cm
'spectroscopic =E=@e In
absorption or emission in classical terms.
2l| The vibrationol energy the mechanism of radiation with which it
levels and obvious if one considers absorb energy only from frequency.
undergoing simple harmonic motion. allowed transitions between them Ihis, again, is vibrating molecule will own oscillation
for a diatomic molecule absorption, for instance, theFig. 1.8) and this must be radiation of its
interact (cf.
In particular, we should notice that the lowest can coherently
or (3.6), is vibrational energy, obtained by putting v:= 0 in Eq. (3.5) 3.1.3/Anharmnonic Oscillator bonds, although
elastic
harmonic motion; real instance,
E= ha.,se, joules (wone, in laws of simple bond between atoms /s stretched, for
not obey exactly the
Hooke'slaw. Ifthe
Hz) Keal molecules do asto obey
are not so homogeneous
 vibrational
energy wherea and A
When withextensions
greater
3.3
Compressions there
64
purely
is Fig. shows,
called (dashed) comes
for fo
Eq. is empirical 3.3 than
(3.1l) a
constant ||
the diagrammatically 10 molecule a
conmpressions.and The the Ssayper sma|
amplitudes. and point
Morse
levels is expression Morse Energy ideal,
used 0.5 D Deaf1.5 cent
for Deq at
function: which
is a curve: simple of
the ft
0.5
instead
particular
found
which bond the it
length-a
the harmonic the wil
to of energy shape bond Fundamentals
beEq.
molecule E= fits (eq) 1.0 break
(3.2) this of may be
De of parabola. -the
(l curve a the
in and diatomic much of
thexp{a(req,
e
- energy taken Molecular
0,x,cm D., to Intermuclear
distance
a more
Schrödinger good molecule curve dissociates as
is
the complicated
elastic,Spectroscopy
perfectly
approximation 2.0
dissociation -r)}] undergoing
for a
(U=0,
equation, typical atoms.
into
behavior
1, 2.5 A
2, eneros.
...) the was anharmonic diatomic tor
Deg
pattern derived mustlarger Thus

together be
molecule. although
of byextensions assumed
the P.
M.
allowed
(3.12) (3.11) Morse. Figue

helow,where
emall
D.

lt
Some and and
shall Ses eue
gnore
hemn. 0,
etc., should Fig3.4 of
positiVe x, 1S
these 1san
rapidlyenergy be thne
OSeulaton
mentioned Energy levels
coresponding
(0.01),
oscillations. The
levels undergoing
anharmonic Dea0.5
minishing vibrational Deq are
require that sketched trequency
so
3 6
in
Eg. energy
that
anharmonicity
magnitude. cubic, (3.12), inthe
(expressed
Yeq.
levels vibrationalSpectroscopy
Fig. Infra-Red
quartic, like 3.4.
and
These etc., Eq. some
constant in
(3.11), wavenumbers)
levels
terms terms transitions
is
an crOwdwhich.
are in Internuclear
distance
importantapproXimation between cm-! more for
bondwhich
them
closely
only with stretching we
at only;
anharmonicity for Dr Do together shall
large more diatomic
a
vibrations,define
values precise with
constants
molecule more
of
expressions
v.
increasing
1S
and clOSely
always 65
we y,
 more
Dopulation. In Lemperature, the andThese. Thus The and nd (V=0).
other
by Thus
systemthe point by
Which Thus a t
putting we
spacing
and normally they selection we postive a we with decreases the comparr rewrite
words, however, see we
restct see
Thus, between are that would zero anharmonic
we only rules frequency that
integral v
= with
the the the Eg.
ourselves lo may are 0,vibrational steadily (312)
population the same for
zero-point have the
predicted may (at
very a use the v
vibrational
th e
lines as the the for be which. oscillator enerpy
for
for anharmonic infinitely with
to
good
Ne Boltzmann of by oscillation defined energy. the
the of energy according levels
thrce he Au=theory the increasing behaves anharmonic
prOimalon,
Cxp(-4.8)
= = levels harmnonic small as Its of Fundomentols
D=0.008 = exp tl, the oscillation
ransitions: and oscillatordiffers frequency the
1 distribution t2, Av= (hypothetical
vibrations to u.like
Slale is, oscillator,
observed harmonic
6.63 Eq. lf oscillator.
wethe
aand slightly of
is tl, are (3.13), harmonic
we 1.3 8 x we wil about frequency now Moleculor
eany 10 shall 3, +2,
oscillator
may x (Eq. at in +3, found from equilibrium
be ) as
10 practice with e
consider
goore O0O x3x10"x10 shortly the
(1.12) .. to that
given the 0)
=
Spectroscopy
23 the equilibrium (in the oscillator
of x most, be (Eg.
300 additional to for by cm)molecule the
allsome to see, have be the Eq.oscillation (3.6)),
ransitions show of hypothetical
one ofrapidly harmonic (3.14).point. would but
observable
order with we
per possibility frequency would
Thus For be an see
riginating cent diminishing
10 oscillator any energy
oscillation
be that
of intensity.cm in at
the of the real of the we
and, larger state the state can
ground
at probability (Eq. ground
anharmonic equilibrium
v= specified frequency
obtained Write
Further, jumps.
at (3.7).
state room state (3.14) (3.13)
l
or

solve one for those linesThese 2. .

when
ne and
@,:ofne Spectral instance, 3.
at v=0’v=2,
w
Or observed
force we any 8347 near lie three v=0’V=3,Av=+3, =0
very
the the find ’
constantabsorption
two 20,
transitions
undamental
very 0. cm'.shows close v=l
fundamental of
= the and
If to AU=
many ofoccurred 2990
three we
a
very 30, 0,, are Av=
other the wish tl,
lconstants cmr=0.0174.
bond equations intense are 20o,,shown =20,(1-3x,cm
) +2, =
diatomic absorptionexactly to called
with
0,(1 with
in find and in with -2x,)
absorption small considerable
and HCI
at (cf. the firstandthe 30,. Fig. =30,(1 normally Spectroscopy
Infra-Red
molecules the frequency
may the equilibrium
w, Eqs. 30, 20,11 3.4. intensity. cm
reduced (l- The To -
4r'ü;euk= beclassical Thus
(1
- - (3.15)): at 4x,) negligible
2886second line good a intensity.
studied =516Nm-! calculated and sewe e
4x) 3x,) 2r) near cm
mass the that, 8347 =5668 = 2886 =frequency approximation,
vibration cm,
byare equilibrium overtones, @, intensity.
intra-red
inserted. directly whereas cmcm! cm! weaker
a is
frequency, of called
the
from respectively.
techniques, These frequency
Eq.
for molecule one the since
for he
t fundamental
at
data, (2.22) real, ideal 5668 x,
are from
together may cm, The 0.01,
collected by harmonic
anharmonic these
inserting differ spectrum
absorption,
and the
with data, three
in considerably.oscillator very
a
Tablethose the molecules we of spectral (3.15c) (3.156) (3.15a)
for value must weak HCI, while 67
3.1. the
a
 simply Wethesince thanThus, instead
transitions
appreciable. Although
Similar t
electronic we3000 while We
consider 4. raised
is Data 68
saw 32temperature
turn Molecule
shall athe refers
cm. high should V= HHBr HCIt HF
sum
the
energies), call that Chapter
the
in
in now fundamental
l
increase
of
’v=2, 1000 from Thus
or
if we the to
IClt NO CO
8 Table3.1
VIBRATING
ROTATOR
DIATOMIC
Since
a
the preceding
temperature
to this the have
of diatomic consider of cm. in vibration *Cl
the
Born-Oppenheimer the the weak the =at, 1gnored isotope
2
separate is energies that (since
sample absorption Au=+1, excited We tolsay,
tantamount molecule section a is 1904.0 2169.7 2309.5 2649.7 2990.6 4138.5
Vibration Some
typical a diatomic one x, may v=2 600 has
transitions 384.1 (cm)
energies: of
when
condition small
is mayKpa
normallycalculate state will become
state
particularly
(i.e.,
aa molecular
Eroal Eotal to
execute two
found
we
can thediatomic
molecule
true a and
0,(1-4x,)cm
arise,
=
population
about
be from Fundadato mentals
approximation
assuming for very the some for
=Erot. =Erot, motions
that
molecule
rotations undergoing band
hotpositive).
their will
it
wavenumber
weak would
300°C)
10 low v=
1 0.0038 0.0073 0.00610.0172 0.0171 0.0174 0.0218
Anharmonicity
Constant diatomic of
t t that
the
occurrence. be perfrequency, to
N,- higher
Molecular
Evib, Eyib.
the
vibrational
and so has
are will Suchfound arise cent molecules
(although,
determSpeinedctroscopy
(cm)joules) increase weak close of 1/N,=o the the states,
combined vibrations differentrotational simultaneous if
this intensity
Their the population constant
Force
energy absorptions to
in vibrational becomes
transition we
nal-vibrational Eq.separations
cf.
quite
weenergy intensity.nature
vibration
and
at of
should 238 1595 1902 314 412 516 966 (Nm) by
(6.1), separations
independently.
may,
may slightly
are
those
asexp(-2.4)
the
of
that,
note if inra-red
as frequency
usually
be from V=1 spectroscopy. d
this first a andconfirmed lower distance
(nmTeg
of
HCI rotation. called v or Internuclear
strictly about
were =0 the
approximation,
y.
This, were1-10
of wavenumbers
totemperatug
0.2321 0.11510.11310.16090.14140.12740.0927

energy byhot 500 v=lA 0.09,

includes raising (3.154)
(3.16) which nearlycm: bands cm! ani
is
Initially, Taking We
t(3.18)
he in is, The rigid,Note,
fact, shall
separation however, rotational however,
Fig.3.5 isonly yet the see
taken we
vibrating! separate later
some no shall
between to levels that
Some attempt ignore in
be
1/1000 expressions what
Energy the are The it is
of two
the same of sketchedatretention not the circumstances
levels scale logical small
tional that
for for
between in in
ofall this Fig. ofD to centrifugal
r
energy given J
and diagram 3.5 wouldignore and Spectroscopy
thisInfra-Red
Jis the
levels v for D distortion &,
approximation
(a
the values. since v the have since from
for consequence
same two only
the this Eqs.
th e
first in Note lowest a constants
two the separation very
implies (2.26) does
that
rational v=0 ofvibrational minor
6
the since that D, and not
4 5
Born-Oppenheimer between effect we
and H, (3.12), apply.
the etc.,
states v levels, are
y=1 rotational
=l on
y=0
treating and respectively,
havewe
of states.neighboring the
a V=0 hence
diatomic spectrum.
constant and the
assumption), v=1.There molecule
write cm
,-l
molecule. J
values
B
in (3.18) (3.17)
Eq. is, 69
as
 quantum
number
upper InspecialalreadyStrictly separately:
acOmpanied It 70
Frg.3.6 Fig. may
state be
3.6. andspeaking.
dealt
and therefore shown
together Some J=0 J
we by rare with
-0 a have a
6 6 double cirumstances, in that
simultaneous
Chapter may we
tronsitions P. we
thdrawn
e
have the
with
Ps for
the v also selection
between
spectrum Pa AJ=-1 the some 0= 2.
state
lower rotational may Note have
P of Av=+1,et+2,c. Fundamentols
asthe carefully, rules
orising the P state J" not Av=0,
ngl-vibrational relevant
change. have for
P isand
conventional the of
from in AJ but
however, Molecular
them.
48 the
energy ) =0; this combined
Ro v=1
levels corresponds
inthat Spectroscopy
R, instate other J=tl
J=+1 a
R, all
diatomic motions
energy branches asand word
cm
- R3 J'.
transitions, to
levels The the are
R4 a
molecule,purely
ofuse vibrational the
of Rs spectroScopy.
a of
desIgnating
same
diatomic
Sy= ] single rotational
V=0
changeexcept those
as
molecule, prime
rotational under
transitions
murr for
for (3.19)
Ver each
tha

ruleAn in
to(Eq.
pression isIt ne
g.Pand
the Called
other
AJ=-1)
n Equation
W,
equally
of to where
negative
itself
be
is 2.
consequence

These AJ=-1, AJ=+1,

1.
Now
we should
brevity,
where,for
We i
thent
analyticalp
eons
pu
energy: inspectrum
general
i
lattiheReeosnm.,ember
labeling -1.
readily the The
m, can : -
(and
So
3.6. contexts, Rare spaced (3.20c), replacing if have ofnotthteheat levels
expression the
R wil two 3.6 . at cf.
for This referred
ofbranch. frequency AJ=-1. that that the -e",u=0
AEj=E' y=1
shown
the
notation, line
not expresSsions (Eq.
transitions
th e Eq.
is we appear. lines then, AE,y= AE,y=
isJ=J+l Bom-oppenheimeris writewe = foot (2.20))
J" taking 0,+
pectrum: that the series shall This to Note + J'=+l (3.18)). for
E= with Lines as represents
(spacing , of
conventional
the called: is theLines in 1AE,,= @, 0, BJ-J)J'+
õ,
th e shown that
Fig .
thapparently
be particularly
Vyper the en P
is Eq. may
- +2BJ" toB for Consideringspectrum
arising concerned usually the
i=nclusion lower quite branch, to
2B)
=
the (3.20a) snect
conveniently be 2B(J' or
J'
orJ be
0, rotational
will
0, the -J"=-1;
+1) hence
identical
(1-2x,). Spectroscopy
occur Infra-Red
notation JJ") fconsistent:
rom arbitrary combined on called that =0, + -J
approximation-rotation
+2Bm of low-frequency
with while each and 1)=+1; J"
ma y
the value A/= m cm only be with
A the J'+ l + cm in +1) levels
- for notation those side cannot 2Bm hence obtained
the varying
4Dm centrifugal such as -2 values vibration-rotation band combined
in cm J=0,
into:
J=0, cm J"
a to of upper v
suthx, the si de the origin be Eq. =0 are
cm specra.
-1 0’v= by
P ofmay zero(3.20b) i
distortion IS
high-frequency
and
0 band
of or m=t1,
1, 1, and applying
filled
become 2, 2,
(n llustrated t2 , origin band since .. . . is
lower varying to
R +1 coresponding has unaffected 1
= in spectrum. th is +2, transition,
t1, constant clearer , centre.would positive the This
+2, on branch S +2addition side but, . . vibrational
+3,...) the if (mEvidently by
selection indicateddegrees is
D to we to since implyvalues we
diagrammatic
leads positive,
state
+l
vibrational
have
states
considered herenegative mit value for
in
to any
schematically
the A/ mthe0,wil AJ=+1
of
is
following spectrum that=+l) changes, a molecular
(that consist
line J' (3.20c) (3.20b) (3.20a)
or direct (3.19))
(3.21) here: later, 71
are is at J"and
 mua
acparate The is ofonly is 72
infra-redhence
Sectuon This
theFrom decrease
from resolution.
gives constant 1 the Fig. also(since
In anharmonicity origin
band negligible However,
3.3
B.
pes waB centre
Fig . band3.7(a),
anharmonicity
allows Since
Pa Pa s the the the
slalaanal 23.1)and the in 3.7(6).
Boung values tabie. tabie
observed in centers a we
moment sat1stactory is
separation with where the to
suon VIBRATION-ROTATION
3.83 MONOXIDE good have
appearance a
came weand some we wethe very
lmes hs we
cm
wavenumbers factor, infra-red seenin
2123.M0 2127 6213163 2135.55 of
see from show can o, high
213943 first,
inertia could,
agreement between lines fundamental 0,(1 =
whcn acpo Table3.2 This that a calculate,
close the of ondegree Chapter
spectrometer
ol the the in overtone -2x,)), the
therefore, immediately fundamental
eaolved Bal and band the the
e
more
2B
inspection of other ofFundamentals
approxmale
Falalmal Separation AV bond, with rotational
the P absorption as
shown bands but, accuracy. that 2B
Portprecise = centre and
3.98 895 3.92 3.88 have the 3.83 first hand,
Thus of length R by has is
value gives of branches
vibration-rotation
is
the
microwaveobtained cm at the lines five in extending
having isresolving some a of
acig infro-red
about lines SPECTRUM the and not Molecular
rolational
asuclie from B 'wings' as
36 next first cm
10
= the
numbered in identicalnegligible.
sbows spectrum infra-red 1.92118
quite 1.915
cm-1
B= 2143
wavenumber each overtone
section,the the
Line values of powerSpectroscopy
is dala R Ro
cm' the branch. selection or
biursod tc go0d rotational
are of band less,
following
cabon data cm spectrum.
while according of It of
npourum
oblainable values OF equilibrium carbon affects about while D
ul alone. derived increases; We of rules
monaxide.
ko
2161.97 2158.31 2154.59 2150.86 2147.08 for
the
shall carbonCARBON structure.
much to monoxide tonot 0.5
an of Historically, the by average is
carbon tronm discuss
this monoxide
their include only cm
cvclope microwave
rotational
later. frequency
line decrease J" This
spectra SeparationAv the it
some
separation shortly values. are Av=+2, is
onoxide
Now constant of is
position obvious
even 3.66 3.72 3.73 3.78 course. studies is under
shown.
illustrated 0.01
thTable
e 0,
we apparent
unde if and 43 per
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4350
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are
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temperature
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anda
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Av AT PR
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carbon can P = of 2096 of
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Molecular
oblained
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the respectively.
J8KTBlhc2B+
resolution.
due 2144 Spectroscopy
carlier was m=J+l hence
the Bhc to
about
separation the Miss
values, +] we All
300
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rotational 2192
substitute Cook
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much We about the fine
intensity
are in University 2241
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cm (3.20c)
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3.8), m been
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can be
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as restrict the high of a APPROXIMATION:
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have
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constant
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Ae= the our an V is will VIBRATIONSsome into thatsee
two @,
discussion in increase quantum same onnot hence
accompanied account,
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that, then l/ is 10° that cmx,=0.0061. vibration
0,(l-2x,). vibrations as varysimple the the
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vibration band
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OF
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harmonic during frequency
+ values the In even by shown @,=2143.26
0,(1-2x,) =
+ B,J'U'+ and increases
fact average the where
anvibrational and THE origin,Infra-Red
Spectroscopy
B)J"AJ=+l fundamental as a, the an more situation increase ofthe THE 20,(1 since
a by inertia
re BORN-OPPENHEIMER the course rotation at
+ B,
small value equation with bond an INTERACTION -3x,) the ofthe
1) 1) and wit h is is energy; mean carbon
+ - rather in the
example and firstmidpoint
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vibrational
the the ofcan
=
with B,, of equilibrium this bond B a overtone
4260.04 anharmonicity
J'=-J"+ 1 vibrationalthe morevibrational constant)single proceed monoxide,
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is of
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> rotational
form:
energy.complex. Section seen rotation, P)
is quite
+
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1, For for energy, 2.3.4, Fig. changes OF
2,cm-! i.e ., Now
independently
be Ro»
this constant each however, to
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...)
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transition an and same

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Fig. other.
(2.32a) level (3.22) upper of 4260.04
3.4. of the this. the that A This, 75
v B