Vibrational-rotational spectrum of HCl

Ana B. Muñoz-García
[email protected]
 Vibrational spectroscopy is one of the most important tools for the accurate
determination of molecular structure

Goals:

1)  Measure the energy of the rotational-vibrational transitions

of HCl in gas phase
and

2)  Use these energies to calculate a set of molecular

and spectroscopic parameters

§  Basis on vibrational and rotational spectroscopy: models

§  FT-IR spectrometer
§  Experimental procedure: generating H35Cl H37Cl D35Cl D37Cl
§  Registering the spectra and collecting data
§  Data analysis
 Basis on vibrational and rotational spectroscopy
The different parts of the electromagnetic
spectrum have very different effects upon
E interaction with matter

Each portion of the electromagnetic spectrum

has quantum energies appropriate for the
excitation of certain types of physical processes.

Ionization Energies ≤ far UV are not sufficient to

Energy
eject electrons from the atoms of the
material: non-ionizing radiation

Visible-near UV light à Electronic transitions

UV-Vis Spectroscopy
Infrared light à Molecular vibrations
Vibrational Spectroscopy

Microwaves light à Rotations

Rotational Spectroscopy

If Infrared energy is supplied, vibrations AND rotations occur:

Vibrations and rotations are coupled à Vibrational-Rotational Spectroscopy
Transition |m> à |n> occurs when :

1) Incident light has the appropriate frequency

2) Probability of transitions is ≠ 0 à Selection Rules

1
E = hν = hc = hcν!
λ
Frequency Wavenumber
(s-1=Hz) Wavelength (cm-1)
(nm)

Diatomic molecule as HCl:

Cl
one can associate two point H
masses that vibrate and rotate
around the mass center m1 m2
 Vibrational transitions Cl
H

Harmonic approximation m1 m2
re
Equilibrium distance

Force constant

ZPE = E(n = 0) ≠ 0
Vibrational quantum number
(ν in some books)

Oscillator
Reduced
frequency mass

m1m2
µ= En+1 − En ν e
m1 + m2 v!n→n+1 = =
hc c
 Among the 3N-6(5) vibrational modes of a molecule of
N atoms, only those where there is variation of the
dipole moment of the molecule are active to the IR

Symmetric Antisymmetric
stretching stretching

Scissoring Rocking Wagging Twisting

Bending
 Among the 3N-6(5) vibrational modes of a molecule of
N atoms, only those where there is variation of the
dipole moment of the molecule are active to the IR

H2O: 3*3-6=3
normal modes

ACTIVE ACTIVE ACTIVE

Mode Frequency (cm-1)

Symmetric Stretch 3390
Antisymmetric 3290
H-O-H Bend 1590
 INACTIVE

CO2: 3*3-5=4 ACTIVE

Degenerated
normal modes
ACTIVE

ACTIVE

Mode Frequency (cm-1)

In-plane bending 670
Out-of-plane-bending 670
Assymmetric Stretch 2300

HCl: 3*2-5=1 ACTIVE

normal mode
 Morse potential

More realistic model

V (r)

Dissociation energy

Anharmonicity
Factor
 Harmonic vs Morse

Equidistant energetic levels Energy difference between levels diminishes

for increasing n à continuum
No dissociation, nmax : En=En+1
No nmax Dissociation!!
Room temperature
only 1ß0 and 2ß0
Room temperature nmax (First overtone/
Only 1ß0 Second harmonic)
(Fundamental / n
First harmonic) n
n
n
n
n
n
Rotational transitions Cl
H

Rigid Rotor m1 m2
re
Rotational quantum number
Moment of
Inertia

!2
EJ = J(J +1) = Be hJ(J +1)
2I e
h
Be = 2 Rotational
8π I e constant

!2
E0 = 0(0 +1) = 0
2I e
 EJ+1 − EJ
v!J→J+1 = = 2Be (J +1)
hc
v!J+1→J+2 − v!J→J+1 = 2Be
 When J increases, the centrifugal force increases
Non-Rigid Rotor à the rotor cannot be considered rigid anymore

Centrifugal correction to the energy: EJ = Be hJ(J +1) − De J 2 (J +1)2

Centrifugal
distortion/stretching
factor
Not to be confused
with dissociation energy De !!!
Vibrational-Rotational transitions

Vibrational and rotational motions are not independent: h

Rotational motion depends on I, which depends on re B= I = µr 2
8π 2 I

h I n = µ rn2 r0 ≠ r1 ≠ r2 ... ≠ rn
Bn = 2
8π I n
For low vibrational quantum number n, linear dependence:

⎛ 1⎞ Rotational-vibrational
Bn = Be − α e ⎜ n + ⎟ coupling constant
⎝ 2⎠ (empirical parameter)

Five contributions:
Harmonic (vibrational) / anharmonic (vibrational) /
Rigid Rotor (rotational) / Centrifuge (rotational) /
Rotational-vibrational coupling
All selection rules for vibrations and rotations combined
In particular
ΔJ = −1 ΔJ = 0 ΔJ = +1
P-Branch Q-Branch R-Branch
(Forbidden)
Lower energy Higher energy

Room temperature:
several J populated for n=0

The rotational fine structure

for each vibrational transition
of each molecule will look
like this:

R P

ν!
 FTIR spectrofotometer
Main components Nerst (YSZ) or Globar (SiC) cylinder
Emits IR radiation when stimulated by
1.  Light Source
electrical current
2.  Michelson interferometer
3.  Sample holder (cell)
4.  Detector

Scan of all frequencies in the radiation :

Beam splitter
Fixed mirror + Mobile mirror (varying optical path length) à
Constructive or destructive interference
Absorbed by the sample à Detector à Signals à Interferogram

Interferogram
Intensity wrt optical path length
 Interferogram Spectrum
Intensity wrt optical path length Intensity wrt wavenumber

+∞ +d
−i2 πν! x −i2 πν! x
I(ν! ) = ∫ F(x)e dx → ∫ F(x)e dx
−∞ −d
Upon truncation A can take
negative values à Unphysical

Accumulation of spectra Apodization No negative signal J

Peak enlargement! L
Get rid of the noise:
-  Noise is casual
-  Signal is coherent
Accumulation of different
spectra cancels out noise
Signal-to-noise ratio improves! J
 ?
In single-beam spectrometers,
we need to register first the “blank”,
i.e. the media without the molecule of interest
Which air molecules are
active to IR?
 Experimental procedure
Rotational-Vibrational spectra depend on μ à
different spectra will be obtained for different isotopes

We will register the spectra of four compounds:

H35Cl H37Cl D35Cl D37Cl

Each species has a unique spectra because the substitution of

different isotopes changes the reduced mass of the molecule

m1m2
µ=
m1 + m2 ?

µ D 37 Cl > µ D 35Cl >> µ H 37 Cl > µ H 35Cl

Which substitution affects
more the spectra?
v!D 37 Cl < v!D 35Cl << v!H 37 Cl < v!H 35Cl
35Cl and 37Cl appear with ~75%:25% relative abundance in Cl compounds

D abbundance is only 0.016% à we need to generate DCl !

To generate D35Cl and D37Cl you will perform a hydrolysis of Butyryl
Chloride with D2O

Liquid Liquid gas

Liquid
+ D2O à + DCl
D
(D35Cl /D37Cl)
(35Cl /37Cl)
H2O
D35Cl D37Cl (partial
H35Cl H37Cl exchange)

Gas cell

Material: NaCl
?
Why not glass or polymeric
transparent material?
? Why do we register the HCl spectra in gas phase and not in solution ?

In condensed phases, the lifetime of each state decreases, so the indetermination of

the exact energy of each state increases à band broadening
!
ΔE • Δt ≥
2
Fine structure (rotational) is lost in IR spectra of condensed phases

In gas phase, the lifetime of each state is long, so the ΔE is small à narrow peaks

For the same reason, in order to see Why we will not determine
more resolved peaks,
we will register the spectra of the first
second harmonics at low
pressure?
?
harmonics also at low pressure
pV = nRT
 Registering the spectra and collecting data
For each specie we
n=0 à n=1 First harmonic
We have D35Cl D37Cl observe two
and and
four species: H35Cl H37Cl vibrational
n=0 à n=2 Second harmonic
transitions:
Total: 8 sets of data
with P-R branches 1) Identify peaks for each
molecule and get their ν!

ν!
 For each specie we
n=0 à n=1 First harmonic
We have D35Cl D37Cl observe two
and and
four species: H35Cl H37Cl vibrational
n=0 à n=2 Second harmonic
transitions:
Total: 8 sets of data
with R-P branches 1) Identify peaks for each
molecule and get their !ν
2à3 4à3
3à4 1à2 3à2 5à4 2) Pair each ! with their
ν
2à1 Δn and ΔJ
4à5
1à0 6à5
5à6 0à1

6à7 7à6

7à8 8à7

ν! n=0 à n=1
 For each specie we
n=0 à n=1 First harmonic
We have D35Cl D37Cl observe two
and and
four species: H35Cl H37Cl vibrational
n=0 à n=2 Second harmonic
transitions:
Total: 8 sets of data
with R-P branches 1) Identify peaks for each
molecule and get their !ν
3 -4
4 2 -3 -5 2) Pair each ! with their
ν
-2 Δn and ΔJ
5
-1 -6
3) Assign a dummy
6 1
variable m to each peak:
7 - Positive for R branch
-7
- Negative for P branch
8 -8

ν! n=0 à n=1
4) Fill two tables for each molecule like this:

First Harmonic H35Cl Second Harmonic H35Cl

n m ν! n m ν!
1 1 2 1
1 2 2 2
1 3 2 3
… … … … … …
1 -1 2 -1
1 -2 2 -2
1 -3 2 -3
… … … … … …
 Data Analysis
Interpolation linear multiple regression of the following equation:

⎛ ν! e χ e ⎞ !
ν! 0→n = ⎜ν! e − ⎟ n − (ν! χ
e e )n 2
− !
α e (mn + m 2
n) − 4 D e m 3
+ (2 B! e − α! e )m
⎝ 2 ⎠

A1 A2 A3 A4 A5

ν! 0→n = A1n − A2 n 2 − A3 (mn + m 2 n) − A4 m 3 + A5m

From A1, A2, A3 , A4 and A5 for each molecule we can obtain:

-  Oscillator wavenumber ν! e
-  Anharmonicity constant χe
-  Rotational-vibrational coupling constant α! e
-  Centrifugal distortion factor D! e
-  Rotational constant B! e
 Once we have ν! e χe α! e D! e B! e of each molecule

we can calculate the following physico-chemical features of interest:

§  Highest vibrational §  Zero-point

quantum number energy (ZPE)

1 ⎛ ν! ν! χ ⎞
nmax = −1 E0 = ⎜ e − e e ⎟ hc
2 χe ⎝2 4 ⎠

§  Dissociation energy §  Spring constant

⎛ ν! e hc ⎞⎛ 1 ⎞
De = ⎜ ⎟⎜ − χ e ⎟ ke = 4π 2 c 2ν! e2 µ
⎝ 4 ⎠⎝ χ e ⎠

§  Moment of Inertia §  Bond length

How these data compare
with data in the literature? h I
I= 2 re =
8π cB! e µ