Molecular Energy Levels and IR Spectroscopy

Absorbance

Emission
E2 E2

DE = hn

DE = hn

E2
Intensity Intensity

E1

Frequency

Frequency
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Molecular Energy Levels Molecules can have the following types of energy
Kinetic (due to motion) Electronic (PE and KE of electrons) Vibrational (oscillation of atoms in bonds) Rotational

All except the KE are quantized

Emolecule = Erotational + Evibrational + Eelectronic

Molecular Energy Levels

Excited Electronic State

Rotational Energy Levels

Vibrational Energy Levels

Ground Electronic State

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Molecular Energy Levels The relative energy of the spacings between energy levels for various types of transitions in a molecule are in the order:
Rotational Transition 1-20 cm-1

<<

Vibrational Transition 2000-4000 cm-1

<<

Electronic Transition 10000-50000 cm-1

Thus the various types of energy transitions occur in different regions of the EMR spectrum and do not overlap
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Molecular Energy Levels Radiation can be absorbed or emitted if the molecule changes any of its energy states
Excited Electronic State

Rotational Energy Levels

Vibrational Energy Levels

Ground Electronic State

Rotational Transition

Vibrational Transition

Electronic Transition

Molecular Energy Levels

Excited Electronic State

Rotational Energy Levels

Vibrational Energy Levels

Ground Electronic State

Rotational Transition
1-20 cm-1 Microwave

Vibrational Transition
2000-4000 cm-1 Infrared

Electronic Transition
10000-50000 cm-1 UV-Visible
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Rotational Energy of a Diatomc Molecule

Rotational Energy of a Diatomc Molecule

Rotational energy is quantized
E = J(J + 1)B J=0,1,2,...

EMR will only be absorbed by polar molecules

e.g. HCl & CO absorb EMR but not H2 and N2

The electrical molecular dipole interacts with the fluctuating electric field of the EMR wave Only certain transition are allowed
12B

DJ = 1

Rotational Microwave Spectrum

6B 2B 0 2B 4B 6B ?
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Vibrational Energy of Diatomic Molecules

The bonds between atoms behave like springs

The atoms vibrate approximately like an harmonic oscillator obeying Hookes Law: F = -k(r req) EPE = k(r req)2
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k is the force constant

Vibrational Energy of Diatomic Molecules

Exchange of PE and KE during vibration

Allowed vibrational energy levels Evib = (v + )hw0 J V = 0, 1, 2,

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Vibrational Energy of Diatomic Molecules

Allowed vibrational energy levels

- cm-1 Evib = (v + )w 0
V = 0, 1, 2,

Allowed transitions Dv = 1 Thus expect only one vibrational peak in the IR spectrum

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Vibrational Spectrum of Diatomic Molecules

Interaction between EMR and the vibrational energy of molecules can only occur if the bond is polar and a change of dipole moment occurs during oscillation. Thus only polar bonds generate peaks in the infrared spectrum of molecules. Thus HCl, CO and HF absorb EMR and have an IR spectrum but H2 and N2 do not.
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Vibrational Energy of Diatomic Molecules

Deviations in the energy profile of a real molecule undergoing anharmonic vibration.

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Vibrational Energy of Diatomic Molecules

Additional allowed transitions and peaks for a real molecule. The first peak is called the fundamental and the additional peaks are the overtones

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IR Spectrum of Carbon Monoxide (CO)

Fundamental Peak

First Overtone

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Fundamental vibration peak in the IR spectrum and the force constants for some diatomic molecules
Note the expected correlation with k and m (refer to equations)

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Vibrational Spectrum of Carbon Dioxide

CO2 molecule

This stretching mode results in no peak because the dipole moment is zero does not change during vibration 18

Vibrational Spectrum of Carbon Dioxide

Asymmetric stretching results in a change in dipole moment during vibration and produces a peak in the IR spectrum.

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Vibrational Spectrum of Carbon Dioxide

The bending mode of vibration gives a peak in the IR spectrum

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Vibrational Spectrum of Carbon Dioxide

Two fundamental peaks are expected plus overtones, combination and difference bands

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Vibrational Modes for Water

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Fundamental IR Bands for Water

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IR Spectrum of Complex Molecules

There are many possible vibrational modes giving rise to complicated spectra with many peaks.
IR spectra are mainly used to identify unknown compounds Peak positions can demonstrate what functional groups are present in the molecule. The peak positions and intensities of an unknown can be compared with the spectrum of known suspects in the same manner that police use fingerprints
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IR Spectrum of Complex Molecules

Two types of vibrational modes are possible:

1. Skeletal vibrations where all the atoms in the molecule move about to some extent.
These vibrations give rise to absorption peaks in the range 700 1400 cm-1 which is called the fingerprint region. 2. Functional group vibrations in which only the atoms in that functional group vibrate appreciably. Each functional group gives rise to an absorption peak at a characteristic frequency, no matter what the rest of the molecule contains. These peaks can be used to identify the functional groups present in the molecules.
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