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Spectral Forms

The document discusses vibrational transitions in molecules, focusing on the effects of infrared radiation on bond stretching and angles, and the harmonic oscillator model for diatomic molecules. It explains the relationship between vibrational frequencies, bond strength, and mass, as well as the differences between IR and Raman spectroscopy, including selection rules and the importance of dipole moments. Additionally, it covers the Beer-Lambert Law regarding absorbance and the factors influencing peak heights and widths in spectroscopic data.

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Liny
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4 views

Spectral Forms

The document discusses vibrational transitions in molecules, focusing on the effects of infrared radiation on bond stretching and angles, and the harmonic oscillator model for diatomic molecules. It explains the relationship between vibrational frequencies, bond strength, and mass, as well as the differences between IR and Raman spectroscopy, including selection rules and the importance of dipole moments. Additionally, it covers the Beer-Lambert Law regarding absorbance and the factors influencing peak heights and widths in spectroscopic data.

Uploaded by

Liny
Copyright
© © All Rights Reserved
Available Formats
Download as PPT, PDF, TXT or read online on Scribd
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Spectral Regions and Transitions

• Infrared radiation induces stretching of bonds, and


deformation of bond angles. Associated with each
vibrational transition for gas phase molecules is a series of
rotational levels leading to more complex rotation-vibrational
transitions

symmetrical symmetrical asymmetrical


stretch deformation stretch
H-O-H (H-O-H bend) H-O-H
Vibrational States and Transitions
• The simplest case is a diatomic molecule. Rotations (2) and
translations (3) leave only one vibrational degree of freedom,
the bond length change, r, a one dimensional harmonic
oscillator

• One can solve this problem exactly as a classical Hook’s law


problem with

– a restoring force: F = –kr and

– potential energy: V=1/2 k(r)2

• Quantum mechanically: Ev = (v+1/2)h ,

  is the vibration frequency


Vibrational States and Transitions

for the simplest harmonic oscillator case (diatomic):

 = (1/2)(k/µ)1/2 where k is the force constant


(d2V/dq2).

– In practice, stronger bonds have sharper (more curvature)


potential energy curves, result: higher k, and higher
frequency.

and µ is the reduced mass [m1m2 / (m1+m2)].

– In practice, heavier atom moving, have lower frequency.

 vibrational frequencies reflect structure, bonds and atoms


Harmonic Oscillator (virtual
state)
Model for vibrational spectroscopy
E
Raman
re
9h
v=4 
r 7
v=3 h
re q 
v=2 5 h

3 h
v=1
Ev = (v+½)h IR h 
1h
v=0
v =  1 

E = h re
1/2k½
Vibrational States and Transitions
• Summary: high mass ==> low frequency

strong bond ==> high frequency

• Some simple examples (stretches in polyatomics):

-C-C- ~1000 cm-1 C-H ~2800 cm-1

-C=C- ~1600 cm-1 C-D ~2200 cm-1

-C  C- ~2200 cm-1 C---N ~1300 cm-1


Polyatomic Vibrational States
• For a molecule of N atoms, there are (3N-6) vibrational degrees of
freedom. This complex problem can be solved the harmonic
approximation by transforming to a new set of normal coordinates
(combinations of internal coordinates, q i) to simplify the potential
energy V—method unimportant for this course
V = V0 + (dV/dqi)0qi + (½) (d2V/dqiqj)0qiqj + . . . . .

• This results in a molecular energy that is just the sum of the individual
vibrational energies of each normal mode: E =  Ei =  (vi
+ ½) hi

• As a result we have characteristic IR and Raman frequencies, i, which


are reflect bond types in the molecule. The frequency pattern forms a
“fingerprint” for the molecule and its structure.

• Variations due to conformation and environment give structural insight


and are the prime tools for Protein IR and Raman.
Dipole Moment
• Interaction of light with matter can be described as the
induction of dipoles, ind , by the light electric field, E:
ind =  E where  is the polarizability

• IR absorption strength is proportional to


fitransition moment between i f

• To be observed in the IR, the molecule must change its


electric dipole moment, µ , in the transition—leads to selection
rules
dµ / dQi  0
• Raman intensity is related to the polarizability,
basimilarly d / dQi  0 for Raman
observation
IR vs. Raman Selection Rules
• At its core, Raman also depends on dipolar interaction, but
it is a two-photon process, excite with 0 and detect s,
where vib = 0 - s, so there are two ’s.
0i• in
need a change in POLARIZABILITY for Raman effect

i
n 0 s
n
0
0

vib = n- 0 = E / h vib = 0- s


Symmetry Selection Rules (Dipole, etc.)

Example:
symmetric stretch O=C=O infrared inactive /Q =
0
Raman Intense Q 
0

asymmetric stretch O=C=O infrared active Q  0

bending O=C=O infrared active Q  0


Complementarity: IR and Raman

IR

Raman

If molecule is centrosymmetric, no overlap of IR and Raman


Vibrational Transition Selection Rules

Harmonic oscillator: only one quantum can change on each


excitation  vi = ± 1, vj = 0; i  j .
These are fundamental vibrations
Anharmonicity permits overtones and combinations

Normally transitions will be seen from only vi = 0, since most


excited states have little population.
Population, ni, is determined by thermal equilibrium, from the
Boltzman relationship:
ni = n0 exp[-(Ei-E0)/kT],
where T is the temperature (ºK) – (note: kT at room temp
~200 cm-1)
Anharmonic Transitions
Real molecules are anharmonic to some degree so other transitions
do occur but are weak. These are termed overtones ( vi = ± 2,± 3, . .)
or
combination bands ( vi = ± 1,  vj = ± 1, . .).
E/De

D0

E01 = hanh

( r - re )/re
Biological systems we generally overlook this, most important in C-H stretch region
Peak Heights
• Beer-Lambert Law:
• A = lc
– A = Absorbance
  = Absorptivity
– l = Pathlength
– c = Concentration
An overlay of 5 spectra of Isopropanol (IPA) in water. IPA Conc.
varies from 70% to 9%. Note how the absorbance changes with
concentration.

• The size (intensity) of absorbance bands depend upon molecular


concentration and sample thickness (pathlength)
• The Absorptivity () is a measure of a molecule’s absorbance at a given
wavenumber normalized to correct for concentration and pathlength – but as
shown can be concentration dependent if molecules interact
Peak Widths
Water
Water

Benzene

• Peak Width is Molecule Dependent


• Strong Molecular Interactions = Broad Bands
• Weak Molecular Interactions = Narrow Bands

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