What is IR spectroscopy?
IR spectroscopy is one of the most widely used and most
important analytical methods in science in general. In
geosciences it is a sensitive tool for mineral identification, since
every mineral has a characteristic spectrum. Further
applications are:
mineral identification
qualitative and quantitative determination of structural
incorporated molecules and defects in minerals, e.g. SiO4,
SiO6, PO4, CO3, OH, H2O, CO2
speciation & concentration
information about atoms and their bonds (e.g., bond
distances)
spatial orientation of dipoles
Molecular vibrations
• How many vibrations are possible (=fundamental vibrations)?
A molecule has as many degrees of freedom as the total degree of freedom
of its individual atoms. Each atom has three degrees of freedom
(corresponding to the Cartesian coordinates), thus in an N-atom molecule
there will be 3N degree of freedom.
In molecules, movements of the atoms are constrained by interactions
through chemical bonds.
Translation - the movement of the entire molecule while the positions of
the atoms relative to each other remain fixed: 3 degrees of translational
freedom.
Rotational transitions – interatomic distances remain constant but the
entire molecule rotates with respect to three mutually perpendicular axes: 3
rotational freedom (nonlinear), 2 rotational freedom (linear).
Vibrations – relative positions of the atoms change while the average
position and orientation of the molecule remain fixed.
Fundamental Vibrations
Selection Rules
The energy associated with a quantum of light may be transferred to the
molecule if work can be performed on the molecule in the form of
displacement of charge.
Selection rule:
A molecule will absorb infrared radiation if the change in vibrational
states is associated with a change in the dipole moment () of the
molecule.
µ = qr
q: electrical charge, r: directed distance of that charge from some defined origin of
coordinates from the molecule.
Dipole moment is greater when electronegativity difference between the atoms in a
bond is greater. Some electronegativity values are:
H 2.2; C 2.55; N 3.04; O 3.44; F 3.98; P 2.19; S 2.58; Cl 3.16
• Vibrations which do not change the dipole moment are Infrared Inactive
(homonuclear diatomics).
Antisymmetrical stretching
Symmetrical stretching
In plane deformation
Scissoring Rocking
Wagging Twisting
Out of plane deformation
Infrared active bonds
The polarity of a bond has a significant impact on the
intensity of an IR absorption band.
Vibrations that cause a significant change in the dipole moment
of a chemical bond lead to strong absorption bands.
Vibrations that result in no change/very little change in dipole
moment lead to very weak or no absorption band.
Symmetrical bonds often exhibit very weak or no absorption
band.
Examples : CO2 No IR absorption
stretching bending
Which of the above stretching
Would this vibrational mode give
modes causes an absorption of
rise to an IR spectrum
infrared radiation?
Symmetrical or asymmetrical
stretching
Yes, the bending motion creates a
net dipole in the direction of the
oxygen atoms as they bend away
asymmetrical stretching
from linearity
Information obtained from IR spectra
IR is most useful in providing information about the presence or
absence of specific functional groups.
IR can provide a molecular fingerprint that can be used when
comparing samples. If two pure samples display the same IR spectrum
it can be argued that they correspond to the same compound.
IR does not provide detailed information or proof of molecular
formula or structure. It provides information on molecular fragments,
specifically functional groups.
Therefore it is very limited in scope, and must be used in conjunction
with other techniques to provide a more complete picture of the
molecular structure.
The acetate anion (CH3CO2-) contains non-linear CO2 group
Asymmetrical stretching Symmetrical stretching
Which of the stretching modes for the acetate ion IR active?
Asymmetrical stretching
Symmetrical stretching
both modes are IR active
Correct answer
Because the C-O vectors are not collinear, the molecule has a permanent
electrical dipole moment that changes when the bonds stretch symmetrically
or asymmetrically
mode D3h activity
ν1 A’1 Raman
ν2 A’’2 IR
ν3 E’ IR-Raman
ν4 E’ IR-Raman
IR BH4-
ν1 ν3
stretch (triply degenerate) IR active
Symmetric stretch IR Inactive
ν2
ν4
Deformation (doubly degenerate) IR Inactive Deformation (triply degenerate) IR active
mode Td activity
3N-6 =3×5-6=9 =1+2+3+3
ν1 A1 Raman
ν2 E Raman
ν3 T1 IR-Raman
ν4 T2 IR-Raman
H2O IR
Symmetric stretch Bending mode Asymmetric stretch
IR active IR active IR active
3652 cm-1 1595 cm-1 3756 cm-1
mode C2V activity
3N-6 =3×3-6=3 =1+1+1
ν1 A1 IR-Raman
A2 Raman
ν3 B1 IR-Raman
ν4 B2 IR-Raman
Given the complexity of the above spectrum, how can we use IR spectroscopy
practically to analyze inorganic compounds?
The example of B2H6 was meant to show that even
relatively simple molecule B2H6 (only has 8 atoms)
produce complicated IR spectra. To explain this further,
consider that a non-linear molecule with n atoms has 3n-
6 normal modes of vibration (that’s 3×8-6 = 18 for
B2H6!!). Fortunately, Group theory can be used to
determine that only 8 of these are IR active. Five bands
were observed between 3000 and 1000 cm-1 and three
bands (974, 951 and 367 cm-1) were not observed
because they were outside the range of the spectrum.
Because of the large number of vibrational modes possible, in
practice one does not analyze the IR spectra of molecules by
predicting and assigning all possible vibrational modes. Rather,
one notes that certain functional groups absorb in certain regions
of the IR spectrum.
IR spectrum of a molecule is very informative and can be used in the
following ways:
(a) To identify the presence (or absence) of functional groups.
The vibrations of certain functional groups (e.g., C–H stretch,
C=O stretch, P–H stretch, etc.) give rise to bands in well-defined
frequency ranges regardless of the type of molecule that contains
them.
(b) As a fingerprint for molecule identification.
An unknown compound can be identified by matching its IR
spectrum with that of a known compound. This type of analysis
can be accomplished by a computer search of data banks of IR
spectra of known compounds. The region below ~1500 cm-1 in
an IR spectrum is particularly useful in this type of search, and
is commonly referred to as the “fingerprint region”. Because of
the complexity of this part of the spectrum, you will be told when
you should attempt assignments within the fingerprint region.
The red complex has well separated νNO bands in the regions
described for the O-bonded (nitrito) linkage isomer while the
yellow complex has νNO bonds that are closer together and fall in
the ranges mentioned for the N-bonded (nitro) form.
IR spectra of metal carbonyl complexes:
