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ABCT4772 20232 A Conglin Handout 3

Molecular spectroscopy is the study of light absorption or emission by molecules, essential for identifying molecular structures and understanding molecular orbital theory. It involves various types of spectroscopy, including microwave, infrared, and electronic, each associated with different energy levels and molecular motions. The document also covers the principles of rotational and vibrational spectroscopy, including models like the rigid rotor and harmonic oscillator, and discusses selection rules and energy levels for diatomic molecules.

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0% found this document useful (0 votes)
29 views37 pages

ABCT4772 20232 A Conglin Handout 3

Molecular spectroscopy is the study of light absorption or emission by molecules, essential for identifying molecular structures and understanding molecular orbital theory. It involves various types of spectroscopy, including microwave, infrared, and electronic, each associated with different energy levels and molecular motions. The document also covers the principles of rotational and vibrational spectroscopy, including models like the rigid rotor and harmonic oscillator, and discusses selection rules and energy levels for diatomic molecules.

Uploaded by

ivan1108lau
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Molecular Spectroscopy

1. Brief Introduction
❑ Molecular spectroscopy is the study
of the spectra obtained by analyzing
the light absorbed or emitted by
molecules. It serves as a crucial
experimental technique for
determining and identifying molecular
structures and forms the empirical
foundation for the development of
molecular orbital theory.
❑ Different energy units used in spectroscopy for different frequency region:
Microwave spectroscopy: Hz
Infrared spectroscopy: cm-1
Electronic spectroscopy: nm
❑ Photo-assisted transition between energy levels

E1 E1

E0 E0

❑ Transition energy:
 E = E1 − E0 = h absorption c =  =    = 1  wave number
 E = E0 − E1 = h emission  E = h =   = 2 angular frequency
❑ Molecular spectroscopy is closely associated with the internal motions of
molecules (generally not consider the nucleus and electron spin)
▪ Translational motion
Whole atom or molecule changes position in 3D space.

▪ Rotational motion Motion of whole molecule


Whole molecule spins around an axis in 3D space.

▪ Vibrational motion
Motion that changes the molecule shape:
stretching, bending, and rotation of bonds.

Motion within molecule

▪ Electron motion
Electrons transition between molecular orbitals.
❑ Energy levels of molecular motion
▪ Translational motion is considered continuous due to too small
energy level interval of ~10-18 eV.

▪ Changes in electronic energy levels are often accompanied by the


changes in both vibrational and rotational energy levels.
▪ Common molecular spectroscopy:
E (energy interval)/eV Wavelength range Spectroscopy
Microwave
Rotational spectroscopy Er = 10-4~0.05 Far infrared-microwave
Far Infrared
Vibrational spectroscopy Ev = 0.05~1 Near infrared-infrared Infrared
Electronic spectroscopy Ee = 1~20 Visible-ultraviolet Ultraviolet-visible
❑ In molecular spectroscopy, whether spectral lines exist (i.e., selection rules)
is usually discussed in terms of whether the molecule has a dipole moment:
▪ Homonuclear diatomic molecules have the dipole moment of 0, so they
have no rotational or vibrational spectra. However, the electronic transition
will change their molecular charge distribution that causes dipole moment, so
vibrational and rotational spectra will be induced.
▪ Polar diatomic molecules have rotational, vibrational and electronic spectra.
▪ For polyatomic molecules that remain non-polar during rotation, like CH4,
BCl3, CO2, etc., they have no rotational spectra but have vibrational and
electronic spectra.

➢ Dipole moment: product of the distance between the positive and negative charge
centers and the amount of electricity carried by the charge center, a vector with the
direction from the positive to the negative charge center.
➢ Polarity: non-uniform charge distribution in a covalent bond or molecule.
2. Rotational Spectroscopy of Diatomic Molecules
2.1 Rigid Rotor Model
m2 R 
m1 r1 r2
m2 R
r1 =
R = r1 + r2 m1 m1 + m2
r1 = R − r2 = R − r1
m2 m1 R
m1r1 = m2r2 r2 =
m1 + m2
2
m m R 1 1 1
I = m1r1 + m2 r2 =
2 2 1 2
=  R Moment of inertia
2
= + Reduced mass
m1 + m2  m1 m2
❑ Compare classical translational motion and rotational motion
▪ Translational motion: mass m, velocity v, momentum p = mv, K.E. T = mv2/2
▪ Rotational motion: moment of inertia I, angular velocity w, angular
momentum M = Iw, K.E. T = Iw2/2
m2
2.2 Rotation of Diatomic Molecules m1
R

2
 1 2 1 2
2 2
1 1 1
Hˆ = −  − 2
 = −  t +  r 
2
m=m1+m2 = +
2m1
1
2m2 2 m 2
  m1 m2
2
− t2 t = Et t Translational motion
2 2  =  t r 2m
−  −
2
 r  = Etotal
2

2
t
2m 2
−  2r r = Er r Rotational motion
2
2
h2
EJ = J ( J + 1) =J ( J + 1) I =  R2
8  R
2 2 2
2I
−  2
 r = Er r
h2 2 R 2
M J = J ( J + 1) 2
4
❑ Energy level of rotational spectroscopy
2
h2 Rotational quantum
EJ = J ( J + 1) =J ( J + 1) = F ( J )  hc = BJ ( J + 1)  hc
2I 8 2  R 2 number J = 0, 1, 2, …

❑ Selection rules
▪ Overall selection rule: non-zero change in dipole moment
▪ Specific selection rule: ∆𝑱 = ±𝟏
∆𝑱 = +𝟏 for absorption spectra
Pure rotation
∆𝑱 = −𝟏 for emission spectra
∆𝑱 = ±𝟏 for rovibrational spectra

❑ Wave number interval for adjacent energy levels


 EJ → J +1 EJ +1 − EJ h h
= = = 2 [( J + 1)( J + 2) − J ( J + 1)] = 2 B( J + 1) B=
hc hc 8 Ic 8 2 Ic
 = 2 B B: rotational constant
❑ Rotational energy level diagram Quantum Energy Level Relative
Number [E/hc, F(J)] Population
▪ The spectrum generated by J=4 20B 9e-20B/kT
transition from one rotational state to
another has a certain wave number
8B
with a sharp spectral line. The
interval of wave number and energy
between adjacent spectral lines is 2B J=3 12B 7e-12B/kT
and 2B (J+1)·hc.
▪ At a certain temperature, the number 6B
of molecules distributed on each
J=2 6B 5e-6B/kT
energy level follows Boltzmann's
distribution. Because the rotational 4B
energy level interval is very small, J=1 2B 3e-2B/kT
the number of molecules in each 2B
J=0 0 1=e-0B/kT
energy level is similar at a given
temperature.
2B 2B 2B 2B
ν
Example: Spectral lines located at 21.18, 42.38, 63.54, 84.72, and 105.91 cm-1 are
presented in far infrared spectrum of 1H35Cl. Determine the moment of inertia and bond
length of the 1H35Cl molecule.

Wave number interval:   21.18 cm −1 = 2B

Then B = 10.59 cm −1
h
I = 2 = 2.643  10−40 g  cm 2
8 Bc
m1 H m35 Cl
= = 1.62668  10−24 g
m1 H + m35 Cl
I
R= = 127.5 pm

Example: Isotope effect. DCl and HCl have the same nuclear distance but different
reduced mass μ and moment of inertia I. Hence, their absorption spectral lines have
different wave numbers, with a weak companion line appearing next to the main line.

h
 = 2 B( J + 1) = ( J + 1) main line
4 R c
2

h
  = 2 B( J + 1) = ( J + 1) companion line
4 R c
2

h 1 1 
Isotope shift:  =  −  = ( J + 1)  − 
4 R c    
2

 
= 2 B( J + 1) 1 − 
  
2.3 Non-Rigid Rotor Model
❑ High-resolution rotational spectra of some diatomic molecules exhibit the
spectral lines that are not exactly equally spaced but in fact converge slowly.
❑ More accurate model for rotational energy levels of diatomic molecules:
EJ = F ( J )hc = [ BJ ( J + 1) − DJ 2 ( J + 1) 2 ]  hc
J = 0, 1, 2, …
 = 2 B( J + 1) − 4 D( J + 1) 3

D << B, D is called centrifugal distortion constant.


❑ Example: for HCl, B = 10.59 cm-1 and D = 0.0004 cm-1.
Transition (J→J+1)  exp (cm −1 )  cal =2B( J + 1)  cal =2B( J + 1) − 4 D( J + 1)3
3→4 83.03 82.72 83.06
4→5 104.1 103.4 103.75
5→6 124.30 124.08 124.39
6→7 145.03 144.76 144.98
7→8 165.51 165.44 165.50
8→9 185.86 186.12 185.94
9→10 206.38 206.80 206.30
10→11 226.50 227.48 226.55
3. Vibrational Spectroscopy of Diatomic Molecules
3.1 Harmonic Oscillator Model R or Re
❑ Vibration of diatomic molecules can be treated m1 m2
as the vibration of a harmonic oscillator.
▪ Two nuclei are stretching and vibrating around their respective equilibrium
positions.
▪ Potential energy is is proportional to the square of distance away from the
equilibrium position (𝑥 = 𝑅 − 𝑅𝑒 ):
1 1 2 1 k
V = k ( R − Re ) = kx k: force constant  0 =
2
fundamental frequency
2 2 2  (→fundamental wave number 𝑣෤0)
▪ Such vibration is equivalent to the vibration of of a mass of μ at Re.
▪ Schrödinger equation
ˆ h 2
d 2
1  h 2
d 2
1 2
H =− 2 + kx  − 8 2  dx 2 + 2 kx  = E
2

8  dx 22
 
3.2 Energy Level of Harmonic Oscillator
 (x) | (x)|2 1 Vibrational quantum
V(x) Ev = (v + )hv
2 number v = 0, 1, 2, …
v=3 E3=7hv/2 1
 1   2 1 1
− x 2
 n ( x) =  n  H n (  2 x )e 2

 2 n!  
v=2 E2=5hv/2
▪ Vibrational energy levels are equally
spaced by a constant ΔE = hv.
v=1 E1=3hv/2 ▪ Wave functions are either symmetric
or asymmetric with respect to x = 0.

v=0 E0=hv/2 ▪ Zero-point energy: E0 = hv/2.


▪ Tunnel effect.
x
❑ Selection rules
▪ Overall selection rule: non-zero change in dipole moment
For diatomic molecules, only polar ones have vibrational spectrum.
▪ Specific selection rule: ∆𝐯 = ±𝟏

❑ The wave numbers of light absorbed or emitted by transitions between


adjacent energy levels are always equal because vibrational levels are
equally spaced: ΔE = hv. (Δ෥
𝒗 = v/c)

❑ For diatomic molecule that can be regarded as a harmonic oscillator, only


one spectral line is present with the wave number 𝑣,
෤ called the characteristic
vibrational wave number (corresponding to the fundamental frequency v0) of
a harmonic oscillator:
1 k
0 =
2πc 
Example: An absorption band at 2140 cm-1 is present in the infrared spectrum of CO.
Considering CO as a harmonic oscillator, determine the force constant in CO bond.
410-4 510-4 6.710-4

% transmission
2140 cm-1

2500 2000 1500


 / cm-1

1 k
Characteristic wave number:  = = 2140 cm −1
2πc 

Then k = 4 2c 2  = 1853 N  m −1
❑ Force constant of some diatomic molecules

Fundamental Force constant


Molecule frequency ν0 / cm-1 k / N·m-1

HF 3958 970
HCl 2886 480
HBr 2559 410
HI 2230 320
CO 2410 1853
NO 1876 1530
3.3 Anharmonic Oscillator Model
❑ Harmonic oscillator is not very precise to describe the vibrational motion of
diatomic molecules, especially for vibrational energy levels with high v values.
❑ The potential energy V = k(R-Re)2/2 is obviously irrational: it cannot increase
infinitely with the increase of R, but should increase to a certain extent then
become zero due to the molecular dissociation into individual atoms.
❑ Morse potential function is introduced for Harmonic
correction: 8 2
 xv 1
0
V ( R) = De [1 − e − ( R − Re ) 2
]  =( 0
) 2
h Morse
❑ Vibrational energy levels from solving
Schrödinger equation: De (dissociation energy)

V
1 1 2 hv0
Ev = (v + )h 0 − (v + ) xh 0 D e =
4x
2 2
❑ Wave number for transition
Ev − E0
= = v 0 [1 − (v + 1) x] x: anharmonic constant R
hc
❑ Selection rules
▪ Overall selection rule: non-zero change in dipole moment
For diatomic molecules, only polar ones have vibrational spectrum.
▪ Specific selection rule: ∆𝐯 = ±𝟏, ±𝟐, ±𝟑, …
∆𝐯 = ±𝟏 — fundamental band
∆𝐯 = ±𝟐, ±𝟑, … — ovetone band
❑ Transitions with v > 1 have much lower intensities.

Transition Spectral band 𝑣෤ ∆𝑣෤ Intensity Change law

0→1 fundamental 𝑣෤0 1 − 2𝑥 Strongest ▪ Spectral line spacing


𝑣෤0 − 4𝑣෤0 𝑥 becomes smaller
0→2 1st overtone 2𝑣෤0 1 − 3𝑥 Weak and smaller.
𝑣෤0 − 6𝑣෤0 𝑥 ▪ Absorption intensity
0→3 2nd overtone 3𝑣෤0 1 − 4𝑥 Very weak becomes weaker
𝑣෤0 − 8𝑣෤0 𝑥 and weaker
0→4 3rd overtone 4𝑣෤0 (1 − 5𝑥) Very weak
Example: From the infrared spectrum of HCl, determine the fundamental wave number
𝑣෤0 , anharmonic constant x, and force constant k in HCl.
T

0→1, fundamental, 𝑣෤0 1 − 2𝑥 = 2885.9 cm-1


0→2, 1st overtone, 2𝑣෤0 1 − 3𝑥 = 5668.0 cm-1

𝑣෤0 = 2989.7 cm-1


𝑥 = 0.0174
𝑣/cm
෤ -1
2885.9 5668.0 8346.9 10923.1 13396.5

1 k 1 k
0 = 0 =
2  2 c 
 k = 4 2  v0 2 = 4 2  c 2 0 2 = 516.3 N  m
4. Rovibrational Spectroscopy of Diatomic Molecules
4.1 Rovibrational Energy Level
❑ When observing HCl vibrational spectrum by a high-resolution infrared
spectrometer, each band is found composed of many spectral lines. This is
because the change in vibrational energy level inevitably causes the
change in rotational energy level.
❑ The intervals between vibrational and rotational energy levels are much
different. The vibration and rotation of diatomic molecules can be treated
completely independent, so the total energy can be regarded as a simple
sum of the two energies. If anharmonic oscillator model for vibration and
rigid rotor model for rotation are employed, the total energy of rovibrational
motion can be expressed as:
1 1 2
Ev, J = (v + )hc 0 − (v + ) xhc 0 + BJ ( J + 1)hc
2 2
4.2 Selection Rule of Diatomic Molecules
▪ Overall selection rule: non-zero change in dipole moment
For diatomic molecules, only polar ones have rovibrational spectrum.
▪ Specific selection rule: ∆𝐯 = ±𝟏, ±𝟐, ±𝟑, …; ∆𝑱 = ±𝟏
❑ Based on ∆𝑱 = +𝟏 and ∆𝑱 = −𝟏, spectral lines are divided into two groups:
▪ R branch: ∆𝑱 = +𝟏 (e.g., E0, J → E1, J+1), on the right
 R = (1 − 2 x) + ( B0 + B1 )( J + 1) − ( B0 − B1 )( J + 1) 2
▪ P branch: ∆𝑱 = −𝟏 (e.g., E0, J+1 → E1, J), on the left
 P = (1 − 2 x) + ( B0 + B1 ) J − ( B0 − B1 ) J 2
▪ If B1 = B0, spectral lines of R and P branch are equally spaced by 2B.
▪ ∆𝑱 = 𝟎 is forbidden, and the Q branch in the middle of R and P branches
does not appear (it appears if molecules like NO have angular momentum
about its axis), with the interval between R and P branches being 4B.
▪ In fact, B1 < B0, with the increase of J, the spectral line spacing decreases
for R branch while increases for P branch.
❑ Rovibrational transition diagram of
diatomic molecules
▪ Rovibrational spectrum can be used
to analyze the structural data of
diatomic molecules, such as
equilibrium nuclear distance Re and
bond force constant k.
▪ The intensity of the component in
rovibrational spectrum is proportional
to the population of the rovibrational
energy level generated by that
component.
▪ Population of J-th energy level can be

Intensity
described by the Boltzmann
distribution.
𝑣෤
Example: On both sides of the center of the rovibrational absorption spectrum of 1H35Cl,
there are several spectral lines with wave numbers of 2925.78, 2906.25, 2865.09, and
2843.56 cm-1, with the overtone at 5668.0 cm-1. What information can be obtained?
Wave number of main (fundamental) band center: 2865.09 2906.25
2906.25 + 2925.78 + 2865.09 + 2843.56
v0→1 = cm −1 2843.56
4 2925.78 5668.0

= 2885.17 cm −1
Overtone band center: v0→2 = 5668.0 cm −1
Anharmonic constant and fundamental wave number:
2885.17 cm −1 = v0 (1 − 2 x) x = 1.728610-2 P branch Q支
P支 Q branch R branch
R支 ~v

5668.0 cm −1 = 2v0 (1 − 3 x) v0 = 2989.01 cm −1


Bond force constant: k = 4 2  c 2 0 2 = 512.5 N  m
Dissociation energy: De = hv0 (4 x) = hcv0 / (4 x) = 8.587 10−19 J
h
From P branch: 2 B = 2865.09 − 2843.56 cm −1 = 21.53 cm −1 = 2  2 2
8  R c
h
Bond length: R= = 126.86 pm
8  Bc
2
5. Vibrational Spectroscopy of Polyatomic Molecules
❑ Vibrational degree of freedom
A polyatomic molecule composed by n atoms has 3n degrees of freedom
and 3n-6 (3n-5 for linear molecules) vibrational degrees of freedom, excluding 3
translations and 3 rotations (2 for linear molecules).
❑ Normal vibration
Molecule vibrates in the basic mode of vibration degree of freedom with all
atoms in phase with the same frequency. It can be divided into two
categories :(i) only bond length changes: stretching vibration and (ii) only
bond angle changes: bending vibration. Various molecular vibrations can be
expressed by the superposition of these normal vibrations.
❑ Selection rules
▪ For infrared spectroscopy: non-zero change in dipole moment
Larger dipole moment change, stronger infrared absorption, infrared active
▪ For Raman spectroscopy: non-zero change in polarizability

❑ Example: H2O with vibrational degree of freedom of 3

Symmetric stretching Asymmetric stretching Bending vibration


❑ Example: CO2 with vibrational degree of freedom of 4

Symmetric stretching Asymmetric stretching

Degenerate

In-plane bending Out-plane bending


❑ Example: Infrared spectrum of n-hexane and 1-hexene
6. Electronic Spectroscopy
Electrons in molecules occupy the
molecular orbitals formed by atomic orbitals.
Electronic transitions between molecular
orbitals generate electronic spectrum with light
absorption or emission, which usually occurs in
ultraviolet-visible regions. Changes in electronic
states also induce the vibrational and rotational
states to change. This gives rise to electronic
spectrum with vibrational and rotational fine
structures and appearing as a band spectrum.
Electronic spectroscopy can provide information on the energy, geometry,
and bonding properties of different electronic states of the molecules
concerned.
6.1 Electronic Energy Level of Diatomic Molecules
❑ Due to the coupling between orbital motion and spin motion of molecular
orbitals, the total state of diatomic molecules cannot be expressed simply by
electron configuration, but must be expressed by the spectral term composed
of the total orbital angular momentum number L and the total spin
quantum number S.
❑ Component of total angular momentum in the bond axis direction:
ML (ML = 0, 1, 2, …)
ML = mλ (orbital quantum number |mλ| = 0, 1, 2 for σ, π, δ orbital)
❑  = |ML| Different  indicates different state energy levels.
States of  = 0, 1, 2, 3, … are represented by , , , , ….
❑ Molecular spectral term: 2S+1
❑ Molecular spectral branch: 2S+1 ( =  + )
❑ In  state, + and - are used for symmetric and asymmetric wave functions,
respectively. For homonuclear diatomic molecules, subscript g and u are
used for center symmetric and asymmetric wave functions, respectively.
❑ Example: O2 molecule.

▪ Electron configuration: (1s)2(*1s)2(2s)2(*2s)2(2pz)2(2px)2(2py)2(*2px)1(*2py)1


Molecular orbitals are fully occupied except (*2px)1(*2py)1.
The two electrons are separated in two different  orbitals, with |mλ| = 1 of 
orbital and spin quantum number s = 1/2 for each electron.

▪ Three pairs of quantum numbers for electron orbital motion and spin motion: 
= 0, S = 1;  = 2, S = 0; and  = 0, S = 0, with corresponding spectral term and
relative energy: 3g- (0.0 eV), 1g (0.98 eV), and 3g+ (1.63 eV).
6.2 Selection Rule
❑ The selection rule for molecules undergoing optical transitions between
different electronic energy levels depends on the transition matrix element:

( ij )  i  j d
 =  *

ϕi and ϕj are corresponding wave functions of transition electronic states, and


μ is the molecular dipole moment function. Only when (μij) ≠ 0, the transition can
be spectrally active.

❑ Selection rule
(1) ∆S = 0; ∆ = 0, 1
(2) ∆ = 0; ∆ = 0, 1
(3) For  state, + + and - - are allowed while + - is forbidden.
(4) u g is allowed while u u and g g are forbidden.
6.3 Electronic Rovibrational Spectroscopy
— Fine Structure of Electronic Spectroscopy
❑ Energy level (after considering electronic state and vibrational transition)
1 1 2
E = Ee + (v + )hc 0 − (v + ) xhc 0
2 2
❑ Transition from low energy level E’ to high energy level E’’ absorbs the
photon with the wave number of
1 1 2 1 1 2
 =  e + [(v'+ ) 0 '− (v' + ) x ' 0 '] − [(v''+ ) 0 ''− (v'' + ) x '' 0 ''] =  00 + ( a ' v' − b ' v'2 ) − (a '' v'' − b '' v''2 )
2 2 2 2
1 1 1 1
 00 =  e + (  0 '−  0 ' x ') − (  0 ''−  0 '' x '')
2 4 2 4
a ' =  0 '− 0 ' x ' b ' = 0 ' x '
a '' =  0 ''− 0 '' x '' b '' =  0 '' x ''
❑ Molecules are usually in the vibrational ground state, so the band series from
v’’ = 0 to v’ has the maximum intensity and is called the zero band series.
6.4 Franck-Condon Principle
❑ The intensity of an electronic transition from v’’ to v’ is related to the wave
functions by 2
I ' "   Ψ v ' R Ψ ν" dτ
*

❑ As electronic transition is extremely fast (10-15


s, much faster than molecular vibrational period
of 10-12 s), the changes in nuclei cannot follow
in such a short time, despite the changes in
electronic states. Therefore, internuclear
distance during electronic transitions can be
assumed constant, which is represented as a
vertical transition in potential energy curve.
This is called the Franck-Condon principle.
❑ Franck-Condon principle states that the transition possibility to the upper
vibrational energy level is proportional to the square of the vibrational
overlap integrals, i.e., Franck-Condon factors.
❑ The vibrational intensity distribution can be used to analyze the geometry of
the excited molecules.
❑ Approximation on separation of rotational, vibrational, and electronic parts:
 =  rot vib el
with ψrot, ψvib, and ψel from rigid-rotor approximation, harmonic oscillator
model, and electronic wave function, respectively.
❑ Franck-Condon principle successfully explain the intensity distribution of zero
band series.
▪ (a) Spectral band intensity
maximizes at v’ = 0 and decreases
when v’ increases;
▪ (b) Spectral band intensity first
increases and then decreases
when v’ increases;
▪ (c) Spectral band intensity is weak
at v’ = 0, then first increases and
then becomes continuous when v’
(a) (b) (c)
increases.

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