Rotacijska spektroskopija

Vibracijska spektroskopija

Dr. Marco Tessari/D. Kirin

Presentation can be found at the website: http://www.nmr.kun.nl/Education

Atomska fizika i spektroskopija Predavanje 8

 Pregled
Uvod: Rotacijska spectroskopija
Momenti inercije
Rotacijski energetski nivoi
Rotacijski prijelazi
Introduction: Vibrational Spectroscopy
Normal Vibration Modes
The vibrational energy levels
Vibrational transitions

Material from Atkins Physical Chemistry 7th Edition, ch. 16.

 Uvod :
Rotational Spectroscopy
 Uvod
Rotacijska spectroskopija koristi EM zračenje u
mikrovalnom području: λ = 30cm − 3mm
ν = 1GHz - 100GHz

Koji uredaji
rade u tom
području?
 Uvod
Osobine:
- primjenjuje se na molekule s dipolnim momentom
- uzorak je u plinovitom stanju

Prednosti:
- visoka rezolucija
- visoka osjetljivost
- nedestruktivna metoda
 Uvod
Primjene:

- proučavanje geometrijskih parametara molekule,

duljine veza, kuteva
- proučavanje planarnosti/ne-planarnosti molekula
- odredivanje elektricnih svojstava molekula
(dipolni i kvadrupolni moment)
- kvantitativna i kvalitativna analiza plinovitih
mješavina (posebno analiza kemijskog sastava u
meduzvjezdanom prostoru)
 Moment inercije
Rotacijsko gibanje molekule može se točno opisati kada znamo
moment inercije.
Moment inercije sistema čestica
(molekule) je dan izrazom:

I = ∑ mi ri 2
i

I je mjera inercije sistema s

obzirom rotacijsko gibanje. Ovisi o
rasporedu mase u sistemu.
 Moment inercije
Ovisno o simetriji molekule,
jedan ili više momenata
inercije moraju biti definirani
da bi se opisala rotacijska
svojstva.
Za molekularne strukture s
niskom simetrijom trebamo
TRI momenta inercije s
obzirom na tri okomite osi.
 Momenti inercije

Kruti rotori se klasificiraju kao:

Linearni rotori : I a = I b , I c = 0 CO, CO 2

Sferni rotori : I a = I b = I c CH 4 , SF6

Simetricni rotori : I a = I b ≠ I c NH 3

Asimetricni rotori : I a ≠ I b ≠ I c H 2O
Rotacijski nivoi
 Rotacijski energijski nivoi
The quantum-mechanical expression for the rotational energy of
a molecule depends on the symmetry of the molecular structure.
For linear rotors only one moment of inertia needs to be defined,
and the corresponding rotational energy is:

h2
E J = J ( J + 1) = J ( J + 1)hcB J = 0,1,2,3,...
2I
h
B= : Rotational Constant (in cm -1 )
4πcI

The same equation applies for spherical rotors. The expression of

the rotational energy for symmetric and asymmetric rotors is
(slightly) more complex and will not be treated.
 Rotacijski energijski nivoi

h2
E J = J ( J + 1) = J ( J + 1)hcB J = 0,1,2,...
2I
M J = 0,±1,±2,...,± J

Energetski nivo rotacije odreden je s dva

kvantna broja (J, MJ).
Rotacijska energija ovisi SAMO o J; to znaci,
za svaki energijski nivo EJ postoji 2J+1 stanja,
tj. svaki nivo EJ je 2J+1-struko degeneriran.
 Rotacijski energijski nivoi
Primjer 1
Rotacijska konstanta 127I35Cl je 0.1142 cm-1. Izračunajte duljinu
veze molekule.

h rICl
B= -1
: Rotational Constant (in cm )
4πcI
m(127I ) ⋅ m( 35Cl ) 2
I = 127 ⋅ rICl
m( I ) + m( Cl )35
h = 6.62608 ⋅10 −34 J s -1
m(127I ) = 126.9045 u
h
m( 35C ) = 34.9688 u h=
2π
1 u = 1.66054 ⋅10 − 27 kg c = 2.9979 ⋅108 m s -1
 Rotacijski energijski nivoi
Primjer 1: rješenje

rICl
h h
B= ⇒I= = 2.451 ⋅10 − 45 kg m 2
4πcI 4πcB
m(127I ) + m( 35Cl ) −12
⇒ rICl = I = 232 . 05 ⋅ 10 m
m( I ) ⋅ m( Cl )
127 35
Rotacijski prijelazi
 Rotacijski prijelazi
EM zračenje može apsorbirati ili emitirati rotacijske prijelaze samo
ako molekula ima permanentni dipolni moment.
Samo polarne molekule daju čisti rotacijski spektar. As a
consequence, homonuclear diatomic molecules and molecule with
spherical symmetry are not directly observable with rotational
spectroscopy.
The intensity of the signals in a rotational spectrum increase with
the molecular dipole moment.
U jeziku IZBORNIH PRAVILA, dozvoljeni prijelazi su definirani
kao:
∆J = ±1; ∆M J = 0,±1;
 Rotacijski prijelazi
The appearance of a rotational absorption spectrum can be
explained using the expression for the rotational energy and the
selection rules:

E J = J ( J + 1)hcB J = 0,1,2,3,...
∆J = ±1 ∆M J = 0,±1

The spectrum consists of a set of lines

at position ν~ = 2( J + 1) B, J = 0,1,2,3,...
with a fixed separation 2B. The
intensity of the lines can be explained
considering the relative population of
the rotational states and their
degeneracy.
 Rotacijski energijski nivoi
∆E >> kT ∆E << kT
E2

E2

E1

E1
Absorbed Intensity

Absorbed Intensity

Frequency Frequency
 Rotacijski energijski nivoi
Primjer 2
Rotational absorption lines from 1H35Cl gas were found at the
following wavenumbers: 83.32 cm-1, 104.13 cm -1, 124.73 cm -1,
145.37 cm -1, 165.9 cm -1, 186.23 cm -1, 206.60 cm -1, 226.86 cm -1.
Calculate the moment of inertia and the bond length of the
molecule.

2h
∆ν~ = 2 B = .
4πcI 1 u = 1.66054 ⋅10 −27 kg
m(1H ) ⋅ m( 35Cl ) 2 h = 6.62608 ⋅10 −34 J s −1
I= 1 rHCl
m( H ) + m( Cl )
35
h
h=
m(1H ) = 1.007825 u 2π
m( 35Cl ) = 34.96885 u c = 2.9979 ⋅108 m s −1
 Rotacijski prijelazi
Exercise 2:Solution

~ 2h 2h
∆ν = 2 B = ⇒I=
4πcI 4πc∆ν~
~ 2h
∆ν = 20.50 cm ⇒ I =
−1
= 2 . 731 ⋅ 10 − 47
kg m 2

4πc ∆ν~
m(1H ) + m( 35Cl ) −12
rHCl = I = 129 . 5 ⋅ 10 m
m( H ) ⋅ m( Cl )
1 35
 Rotacijski prijelazi
Exercise 3
Is the bond length in 1HCl the same as in 2HCl? The wavenumbers
of the J = 1 ← 0 rotational transition for 1HCl and 2HCl are
20.8784 cm-1 and 10.7840 cm -1, respectively.

2h m( 2H ) = 2.0140 u
ν~1← 0 = 2 B =
4πcI
1 u = 1.66054 ⋅10 − 27 kg
m1 ⋅ m2 2
I= r h = 6.62608 ⋅10 −34 J s −1
m1 + m2
h
m( H ) = 1.007825 u
1
h=
2π
m( 35Cl ) = 34.96885 u
c = 2.9979 ⋅108 m s −1
 Rotacijski prijelazi
Exercise 3: Solution
2h 2h
ν~ = ~
;ν 2 HCl =
4πcI 1 HCl 4πcI 2 HCl
1
HCl

ν~ HCl I
= = 1.93605
1 2
HCl
~
ν HCl I
2 1
HCl

m( 2H ) ⋅ m( 35Cl )
2 2
I 2 HCl m( H ) + m( Cl ) 2 HCl
2 35 r r
= =
2
HCl
1 . 94400
I 1 HCl m(1H ) ⋅ m( 35Cl ) r12HCl r12HCl
m(1H ) + m( 35Cl )
r22HCl 1.93605
1.94400 2
= 1.93605 ⇒ r2 HCl = r1 HCl = 0.99795 ⋅ r1 HCl
r1
HCl
1.94400
Vibracijska Spektroskopija
Kod vibracijske spektroskopije EM zračenje koje se
upotrebljava je u infracrvenom (IR) području spektra:

λ = 0.3mm − 0.1µm
ν = 1011 Hz - 1014 Hz
 Uvod
Osobine:
- dipolni moment se mora mijenjati pri vibraciji
- primjena u krutim, tekućim i plinovitim uzorcima
Primjena:
- široka primjena
- visoka osjetljivost
- ne-destruktivna tehnika
 Uvod
Primjene:
- odredivanje duljine veza
- odredivanje snage veza
- odredivanje energije disocijacije
- kvalitativna i kvantitativna kemijska analiza
Normalni modovi
 Normalni (vibracijski) modovi
In general, the description of a molecule
consisting of N atoms requires 3N
coordinates.
• 3 koor. → translacija
• 3 koor. (2 za lin. mol.) → rotacija
• 3N – 6 (3N – 5 za lin. mol.) → relativno
gibanje atoma, tzv. vibracijski modovi
 Normalni vibracijski modovi
Normalni modovi 3N – 6 (or 3N – 5)
♀ pojednostavljen opis mol. vibracija
♀ svaka jezgra vrsi harmonijsko titranje oko ravnoteznog polozaja
♀ sve se jezgre gibaju istom frekvencijom, u fazi su, a centar mase je
nepromjenjen

Primjer: CO2 modovi vibracija

 Rotacijski prijelazi
Exercise 4

Koliko normalnih modova vibracija imaju sljedece molekule:

H2O, H2O2, C2H4 , HC≡C–C≡CH ?

N vib = 3 N − 6 ili N vib = 3 N − 5

 Rotacijski prijelazi
Exercise 4:Solution

N vib = 3 N − 6 or N vib = 3 N − 5

N ( H 2O ) = 3 ⇒ N vib ( H 2O ) = 3
N ( H 2O2 ) = 4 ⇒ N vib ( H 2O2 ) = 6
N (C2 H 4 ) = 6 ⇒ N vib (C2 H 4 ) = 12
N ( HC ≡ C − C ≡ CH ) = 18 ⇒ N vib ( HC ≡ C − C ≡ CH ) = 13
 Normalni (vibracijski) modovi
Svaki normalni mod vibracije je u
stvari harmonijski oscilator koji
odgovara jednoj normalnoj
koordinati. Normalna koor. se
konstruira tako da odrazava sve
individualne pomake jezgri.

Linearna dvoatomna molekula →

• JEDAN normalni mod
• jedina koordinata – promjena
Normalna koordinata
udaljenosti
Vibracijski energijski nivoi
 Vibracijski energijski nivoi
Jednostavni model – HARMONIJSKI
OSCILATOR opisuje dvoatomnu
molekulu:
1 2
(V = kx ) x = R − Re
2
U ovom slucaju, dozvoljeni vibracijski
energijski nivoi su dani s:
1 1
Ev = ( v + ) hω = ( v + )hcν~ = G (ν~ )hc
2 2
v = 0,1, 2,...
1
ν~ = ω
2πc
 Vibracijski energijski nivoi
Dozvoljeni energetski nivoi ► ekvidistantni s

hω
Kutna frekvencija titranja ω ovisi o
atomskim masama i konstantama sila m1 m2
oscilacija:

k mm
ω= , meff = 1 2
meff m1 + m2
 Vibracijski energijski nivoi
The harmonic oscillator is an acceptable approximation only for
small deviation from the equilibrium internuclear distance
(vibrations of small amplitude).
For larger deviations (anharmonicity) the
internuclear potential energy is better
described by a Morse potential:

V = hcDe { 1 − exp(− a ⋅ ( R − Re )}
2

meff ω 2
a=
2hcDe
 Vibracijski energijski nivoi
When the Morse anharmonic potential is used, the permitted
vibration energy levels are defined by the expression:
 1 1 2 ~
Ev = hc ( v + ) − xe ( v + ) ν = hcG (ν~ )
 2 2 
v = 0,1, 2,..., v max
a 2h ν~
xe = = : anharmonicity constants Do
2 µω 4 De De

Note that the energy levels are no longer equally

spaced. In addition, the number of vibrational
levels is finite: for energies larger than Evmax
dissociation of the chemical bond takes place.
 Vibracijski prijelazi
Exercise 5
The 1H35Cl molecule is quite well described by the Morse potential.
Assuming that the potential De does not change on deuteration,
predict the dissociation energies D0 of 1H35Cl and 2H35Cl.
 1 1 
Ev = hc ( v + ) − xe ( v + ) 2 ν~
 2 2 
D0 = De − E0
Do
De

De = 5.33 eV h = 6.62608 ⋅10 −34 J s −1

ν~ = 2989.7 cm −1 c = 2.9979 ⋅108 m s −1
xeν~ = 52.05 cm −1 1eV = 1.602177 ⋅10 −19 J
 Vibracijski prijelazi
Exercise 5: Solution

For 1HCl:
52.05
xe = ~ = 0.01741
ν
1 1 ~
E0 = hc − xe ν = 2.9436 ⋅10 − 20 J
2 4
De = 5.33 eV = 8.5396 ⋅10 −19 J
D0 = De − E0 = 8.2452 ⋅10 −19 J = 5.15 eV
 Vibracijski prijelazi
Exercise 5: Solution
1 k
ν~ = 2989.7 cm =−1

2πc
1 1
HCl
meffHCl
k = (2πc ⋅ν 1 HCl ) ⋅ meffHCl
~ 2 1

1
1 k meffHCl
ν~ HCl = = ν~1 HCl = 2144.3 cm −1
2πc
2 2 2
meffHCl meffHCl

1 1
E0 = hc − xe ν~2 HCl = 2.1111 ⋅10 − 20 J
2 4
D0 = De − E0 = 8.3284 ⋅10 −19 J = 5.20 eV
Vibracijski prijelazi
 Vibracijski prijelazi
♂ EM radiation can induce vibrational transitions only for vibration
modes that induce changes in the molecular dipole moment.
♂ Such vibrations are called infrared active.
♂ The stretching vibration in heteronuclear diatomic molecule is always
infrared active.
♂ Conversely, such a vibration is infrared inactive for homonuclear
diatomic molecules – homonuclear diatomic molecules are transparent to
infrared radiation.
♂ For complex molecules, an analysis of the symmetry of the normal
modes is necessary to define the active normal modes.
♂ The intensity of the signals in a vibrational spectrum increase with the
molecular dipole moment.
 Vibracijski prijelazi
Izborna pravila dozvoljeni prijelazi za harmonijski oscilator:
∆ v = ±1
From the Boltzmann distribution it follows that for almost all
molecules only the vibrational ground state (v=0) is populated at
room temperature (kT=207 cm-1). The IR absorption spectrum is
then dominated by the
fundamental transition
from the ground state to

Absorbed Intensity
the first vibrational excited
state (1 ← 0) .

∆G1←0 = ∆G1/ 2 = ν~ =
1 k
= ν~
2πc meff wavenumber (cm-1)
 Vibracijski prijelazi
Exercise 6
Calculate the relative number of Cl2 molecules in the ground and
first vibrational state at 298 K and 500K

ν~ = 559.7 cm −1
h = 6.62608 ⋅10 −34 J s −1
∆E1←0 = hc∆G1/ 2 = hcν~
c = 2.9979 ⋅108 m s −1
Ei
−
n Ei ∆E k B = 1.38065 ⋅10 − 23 J K −1
=e
kT −
Ej
=e kT
nE j −
e kT
 Vibracijski prijelazi
Primjer 6: Solution

ν~ = 559.7 cm −1
∆E1←0 = hc∆G1/ 2 = hcν~ = 1.1118 ⋅10 − 20 J
N v =1  ∆E1←0 
T = 298 K : = exp −  = 0.067
N v =0  k B ⋅ 298 
N v =1  ∆E1←0 
T = 500 K : = exp −  = 0.200
N v =0  k B ⋅ 500 
 Vibracijski prijelazi
Exercise 7
The wavenumber of the vibrational fundamental transition of
1H35Cl is 2990.95 cm-1. Calculate the force constant of the bond.

1 k
∆G1←0 = ∆G1/ 2 = ν~ = 1 u = 1.66054 ⋅10 −27 kg
2πc meff
h = 6.62608 ⋅10 −34 J s −1
m(1H ) ⋅ m(35Cl )
meff = 1 h
m( H ) + m( 35Cl ) h=
2π
c = 2.9979 ⋅108 m s −1
m(1H ) = 1.007825 u
m( 35Cl ) = 34.96885 u
 Vibracijski prijelazi
Exercise 7: Solution

~ 1 k
∆G1←0 = ∆G1/ 2 =ν =
2πc meff
m(1H ) ⋅ m( 35Cl ) − 27
meff = 1 = 1 . 62665 ⋅ 10 kg
m( H ) + m( Cl )
35

k = (2πν~ ⋅ c ) ⋅ meff = 516.3 N m −1

2
 Vibracijski prijelazi
☺ If the molecules are brought into vibrational excited states, emission signals
involving other energy levels than 0 and 1 can be observed.
☺ In the harmonic approximation these emission signals should appear at the
same frequency.
☺ In reality, they are observed at slightly different positions as a consequence of
the breakdown of the harmonic approximation:

∆Gv +1→ v = ∆Gv +1/ 2 =

2 xeν~
= ν~ − 2( v + 1) x ν~
e

Emitted Intensity
wavenumber
 Vibracijski prijelazi
IZBORNA PRAVILA ∆v = ±1 is derived assuming a parabolic
curve for the potential energy curve (harmonic oscillator
approximation). When anharmonicity is taken into account, the
selection rule ∆v = ±1 does not hold rigorously, and in fact all values
of ∆v are allowed. Experimentally this is confirmed by the
presence of weak bands
(overtones) in the

Absorbed Intensity
absorption spectrum,
corresponding to the
transitions 2 ← 0, 3 ← 0 ,
etc.

ν~
wavenumber (cm-1)
 Vibracijski prijelazi
The sum of the all the vibrational transition energies of a diatomic
oscillator corresponds to the bond dissociation energy D0:

Do = ∆G1/ 2 + ∆G3 / 2 + ... =

= ∑ ∆Gv +1/2
v

Therefore, when several

vibrational transitions are
detectable, the dissociation
energy of the bond can be
estimated (with the so-
called Birge-Sponer plot,
for example).