Point Group

Download as pdf or txt
Download as pdf or txt
You are on page 1of 16

INORGANIC CHEMISTRY - FINALS

VIDEO 4. PROPERTIES OF MATHEMATICAL GROUPS


Properties of Mathematical Groups
● A point group is an example of an algebraic structure
called a group. It is a collection of elements that obey
certain algebraic rules.
● These rules give rise to the properties of Mathematical
groups.
● The four key rules that define a group are: ● A 3x3 multiplied to a column matrix results in a simple
1. IDENTITY - Each group contains an identity operation column matrix.
that commutes with all other members of the group
and leaves them unchanged. (i.e., EA = AE = A).* ● Each symmetry operation can be represented by a 3x3
● Operate (multiply) from right to left, as with matrix that shows how the operation transforms a set of
matrices. x,y, and z coordinates.
● Commutes - if you take the identity and ○ Converts the original coordinates into the
some other operation, A, performing it in new coordinates after the operation.
different orders does not matter. It gives an
unchanged A. Let’s consider C2h {E, C2, i, σh}

2. INVERSE - Each operation has an inverse operation


when combined, yields the identity when multiplied
together. For example, in C3v {E, 2C3, 3σv}
● σvσv = E and C3C32 = E

3. CLOSURE - The product of any two operations in


the group must also be a member of the group. For
example, in C4v {E, 2C4, C2, 2σv, 2σd} ● The convention is to always put the principal axis as the Z
● C4C4 = C2, C4σv = σd, σdσv = C4, etc. axis.
● Taking a binary product would result in an ● The X and Y is the molecular plane.
operation that is already a member of the
group. E
● It is all 1 along the principal diagonal.
4. ASSOCIATIVE - The associative law of multiplication
holds. C2
● A(BC) = (AB)C
● It does not matter which is combined, as
long as it is done in the same order, it gives
the same results.

*Operate (multiply) from right to left, as with matrices.


● X and Y are affected while Z is unaffected because it is
Matrices and Matrix Multiplication
happening along the Z axis.
● A matrix is an array of numbers, Aij
● There are only elements along the diagonal of the
matrix.

● Interested in matrices with equal number of rows and


columns.
● To multiply two matrices, add the products, element by
elements, of each row of the first matrix with each ● Everything is converted to negative.
column in the second matrix.
σh
● Results in a 1,1, -1 transformation matrix.
● It is only the z axis plane that would change.
INORGANIC CHEMISTRY - FINALS
Representations of Groups ● Each column corresponds to a symmetry
● The set of four transformation matrices forms a matrix operation/classes.
representation of the C2h point group. ● Irreducible representations cannot be further simplified
because they are based on the simplest components of
the matrix.
● The point group designation is always given at the
upper left corner.
● These matrices combine in the same way as the
operations, e.g.,

● The matrix multiplication gives us the exact same answer


if we multiply two of the operations.
1 = symmetric (unchanged); -1 = antisymmetric (inverted);
0 = neither
● The set of four transformation matrices forms a matrix
representation of the C2h point group.
Example:

● Take the information in the matrices and tabulate it into


reducible groups by formulating a character table.
● The sum of the numbers along each matrix diagonal (the
character) gives a shorthand version of the matrix
representation, called 𝚪. ● X and Y have identical characters

𝚪 is a reducible representation because it can be further


simplified.
● The transformation matrix is condensed into a simple 4 ● The two Bu in table will be merged forming only two rows
number set. for the irreducible representation.
● Explains how x,y and z coordinates at the center of the
molecule transform with the four different operations.
● Irreducible representations - basic building blocks for
symmetry.

Irreducible Representations
● The transformation matrices can be reduced to their ● Indicate that both x, and y have the same symmetry by
simplest units (1x1 matrices in this case) by block placing it in the same coordinate.
diagonalization.

● Block diagonalize each 3x3 matrix into three individual 1x1


matrices.
● Make a table of the characters of each 1x1 matrix for each
preparation:
INORGANIC CHEMISTRY - FINALS
CHARACTER TABLES AND ONE APPLICATION OF
SYMMETRY 10:28
Character Table - List of the complete set of irreducible
representation (rows) and symmetry classes (columns) of a
point group

Ag Ag Au

● The convention is to always put the principal axis as the Z


axis.
● e.g., the dx2-y2 and dz2 orbitals are Ag, while the pz orbital is
Au)
The first column gives the Mulliken label for the
representation RULES: Properties of Character Table
● Order (h) - The total number of symmetry operations.
● A or B = 1x1 representation that is: ○ h = 4 in this case
○ Symmetric (A) to the principal axis. ● Operations belong to the same class if they are identical
○ Anti-symmetric (B) to the principal axis. within coordinate system accessibility by a symmetry
● E = 2x2 representation (character under the identity will be operation. One class is listed per column.
2) ● # irreducible representations = # classes (tables per
● T = 3x3 representation (character under the table will be 3) square).
○ Same number of rows and columns.
● Point Groups with Inversion (i) ● One representation is totally symmetric (all characters =
○ g - gerade (symmetric) 1).
○ u - ungerada (antisymmetric) ○ Usually the first column.

● If present, number subscripts refer to the symmetry of the ● h is related to the characters (χ) in the following two ways:
next operation class after the principal axis and after
inversion, if present (reflection plane).
○ 1 - Symmetric
○ 2 - Anti-symmetric
Vertical
★ These a for point groups with more symmetry classes. ● The order is equal to the sum of the characters under the
E operation, squared, for each individual irreducible
● The last two columns give functions (with an origin at the representation (i)
inversion center) that belong to the given representation
(e.g., the dx2-y2 and dz2 orbitals are Ag, while the pz orbital is
Au)
○ Indicate functions that have the same
symmetry as the irreducible representations.
Horizontal
● The order is equal to the sum of the characters for all
different symmetry operations, squared.

*where i and R are indices for the representations and the


symmetry operations

● Irreducible representations are orthogonal:


● Translations (Column 3) - x, y, z
○ Movement of molecules through space

● Rotation (Column 3) - Rx , Ry , Rz (with respect to their


individual axis.)
○ Symmetry of the rotations for a 3D molecule. ● Multiplying the all characters of one symmetry class (i) to
another symmetry class (j), getting the sum would equal to
● Quadratic (Clumn 4) - binary products (e.g., x2, y2) zero.
○ Indicates they symmetry of the d-orbitals
have in a particular point group.
INORGANIC CHEMISTRY - FINALS
● There is coupling in a C3 operation wherein x and y are
coupled together.
○ The eventual x and y coordinates depend on
the original x and y coordinates.
On block form:
Should Equal to Zero

Let’s use the character table properties to finish deriving the


C2h table from the transformation matrices, we had:
x and y are not independent in C3v - we get 2x2 (x,y) and 1x1
(z) matrices

● The sum of x and y along the diagonal for each symmetry


operation:
There must be four representations and one is totally ○ E-2
symmetric, so: ○ C3 - -1
○ σv - 0

● The fourth representation must be orthogonal to the other


three and have χ(E) = 1.
○ The only way to achieve this is if χ(C2) = -1.
χ(σh) = -1, giving a Bg. ● The third representation can be found from orthogonality
and χ(E) = 1.
○ Obtained by getting a number to make the
sum of the products for each symmetry
operation is equal to 0.

● C3 and C32 are identical after a C3 rotation and are thus in


the same class (2C3).
● The three mirror planes are identical after C3 rotations →
same class (3σv)
C3v Character Table
● The E representation is two dimensional (χ(E) = 2), mixing
x,y. This is a result of C3.
● x and y considered together have the symmetry of the E
representation.

Orthogonality (Solve here:)

● C3v has two C3 rotations which results in an equivalent


molecule:
○ C3
○ C32 SUMMARY:
● Each molecule has a point group, the full set of symmetry
● The characters for A1 and E come from the transformation operations that describes the molecule’s overall
matrices: symmetry.
○ The E is a 2x2 matrix which contains two ○ You can use the decision tree to assign point
characters under each operation. groups.
● Character tables show how the complete set of irreducible
representations of a point group transforms under all of
the symmetry classes of that group.
○ The tables contain all of the symmetry
information in convenient form.
● The rotation is around the z-axis making z as 1.
○ We will use the tables to understand bonding
and spectroscopy.
INORGANIC CHEMISTRY - FINALS
Using Symmetry: Chirality ● We can use character tables to determine the symmetry of
● One use for symmetry is identifying chiral molecules. all 18 motions (modes of motion) and then assign them to
○ Chiral - a molecule must lack an improper translation, rotation or vibration.
rotation axis (S). ○ We can also tell which vibrations are IR or
○ A molecule to be chiral must be in the C1, Cn, Raman active.
or Dn point groups ● A character table can tell whether a given vibration
■ There should be no mirror plane corresponds to absorption of infrared radiation.
and i. (remember that σ = S1 and i = ○ Does it show a peak in an infrared spectrum
S2) or in a Raman spectrum.
● The infrared and Raman spectra are important in order to
assign fingerprints to molecules.
○ Bond Distances
○ Bond Strength
○ Bond Angle

Procedure:
How to tell the symmetry of all the different possible
motions in the Molecule
1. Assign x,y,z coordinates to each atom.
A SECOND APPLICATION OF SYMMETRY
Using Symmetry: Vibrational Spectroscopy
IR and Raman spectra can be interpreted using symmetry
● For nonlinear molecules, the number of vibrational
modes is 3N - 6, where:
○ N = Number of atoms
○ 3N = Number of degrees of freedom.
● For linear molecules, the number of vibrational modes
would be 3N - 5.
2. Determine how each axis transforms for every class of
● Each atom has three degrees of freedom at minimum. It
symmetry operation in the group.
can move in the X, Y, or Z axis.
○ If an atom moves, the character for all of its
Example:
axes is 0.
● Consider N2O4 which is D2h.
○ If an atom is stationary and the axis
direction is unchanged, its character is 1.
○ If an atom is stationary and the axis
direction is reversed, its character is -1.
3. Sum the characters in each class to determine the
reducible representation 𝚪.
○ Reduce it into its irreducible representation.

● The molecular plane is the x,y plane.


● Each of the six atoms can move in three dimensions.
○ If all atoms move the same amount in the
same direction the molecule moves, which ● Generate the reducible representation for each of the
is a translation, not a vibration (accounts for different operations.
three degrees of freedom).
■ The molecule moves in space.
○ Molecules can also rotate around the three Identity (E) All 18 axes are unchanged.
orthogonal axes, the x,y, and z (which
Answer: 18
accounts for three more degrees of
freedom). C2 (z) All of the atoms in the
○ Therefore gives 3 movements and 3 molecule move giving 18
rotations having a total of 6 in the 3N - 6 zeroes.
formula.
● So for N2O4 we predict that there will be (3N - N) 3N - 6 = Answer: 0
12 vibrational modes.
C2 (y) All of the atoms in the
molecule move giving 18
● A linear molecule only has 2 rotations. A rotation in the zeroes.
axis of the molecule is not considered to be a rotation as it
does not do anything. Answer: 0
○ This results with 3N - 5.
INORGANIC CHEMISTRY - FINALS
C2 (x) The oxygens move but the
nitrogen is stationary.
N’s x unchanged
N’s y,z reversed

Answer: 2 - 4 = -2

Inversion (i) All atoms move

Answer: 0

𝜎(xy) All x and y axes do not


move, but the z axis moves
into the negative. ● The result of IRR should always be zero or a positive
Z axes reversed integer. There should be no decimals.
X, Y axes unchanged

Answer: 12 - 6 = 6

𝜎(xz) Oxygenz move.


N’s x,z unchanged
N’s y reversed

Answer: 4 - 2 = 0

*The oxygens move, do not


assign any character. ● The result of the sum of IRR should match the character of
the Identity Operation of the 18 x 18 matrix.
𝜎(yz) All atoms move.

Answer: 0
5. Use the character table to subtract the translations and
Answer: rotations, leaving the representations corresponding to the
vibrations.
● Each of the 18 irreducible representation corresponds
to a kind of motion either:
● Built in the reducible representation are all of the ○ Translation
irreducible components. It is a sum of irreducible ○ Vibration
components to give the total reducible representation. ○ Rotation
● Decompose it into its essential components. ● The last two column in the character table tells the
symmetry property of translation, vibration or rotation.
4. Now reduce 𝚪 to its irreducible components using the ○ Remove one from the total reducible
character table and the following property of groups. representation.
★ Rotation - Rx, Ry, Rz

1
#IRR = Σ[(# 𝑜𝑝𝑒𝑟𝑎𝑡𝑖𝑜𝑛)(𝑔𝑖𝑣𝑒𝑛)(𝑐ℎ𝑎𝑟𝑎𝑐𝑡𝑒𝑟 𝑡𝑎𝑏𝑙𝑒)]
𝑜𝑟𝑑𝑒𝑟 ★ Translation - x, y, z

● Use the character table of D2h.


● Order - The total number of symmetry operations in the
point group. Vibrational modes (all that remain) =

These are the symmetries of the 12 vibrational modes of


N2O4

Let’s consider the vibrational modes of N2O4 in a little


more detail.
● In all types of vibrations, there is motion for all of the
atoms in the molecule, but we name it according to its
major motion.
INORGANIC CHEMISTRY - FINALS
● The actual vibrations of a molecule are happening very Example:
quickly that you cannot actually see it vibrate. Ethylene (D2h) - 12 Vibrational Modes

● Using the table, we can guess what these modes might


look like physically.
○ E.g., the three Ag modes are totally
symmetric:
Symmetric Stretch (Ag)
Ag Mode

● They are moving in and out in coordination with one


● NO2 symmetric stretch - all the oxygens moving away in another.
the same fashion, wherein it moves out/in at the same ● It retains all of the symmetry operations and classes of
time. D2h.
○ The symmetry of the molecule remains as
D2h and does not change. Symmetric Bend (Scissoring) (Ag)
○ Considered as an Ag mode.
● NO2 symmetric bend - the oxygens are moving in
coordination, but the NO2 groups are bending (scissoring)
in an open-close manner.
○ Leads to a total retention of symmetry.
○ Considered as an Ag mode.
● N-N stretch - most of the motions are along the nitrogen ● Scissoring causes the hydrogens to be moving in
bond. coordination.
○ Compression and Decompression retains all ● It retains all of the symmetry operations and classes of
of the symmetry properties of D2h. D2h.
Au Mode
● This mode is symmetric w.r.t C2 but antisymmetric w.r.t. σ C-C Stretch (Ag)
and i.

● The majority of the motion is along the C=C bond


● Torsion - bending around the N-N bond. The bonds along
the oxygens partially rotate. CH2 Twisting (Au)
○ This breaks the D2h as it is vibrating back
and forth.
○ Vibration at any position, the C2 operation
leads to something that is symmetric, but the
inversion and reflection are anti-symmetric.

● The CH2 groups are moving back and forth.


● Stopping the motion of the molecule makes it no longer a
planar molecule and indicates that it is no longer D2h.
INORGANIC CHEMISTRY - FINALS
Asymmetric Stretch

*Note: Any molecule that has 6 atoms in the presented


molecular geometry and is D2h has the 12 vibrational modes.

All vibrations in a molecule are explained as a sum of the


individual fundamental vibrational modes.
*Note that the Au mode is IR and Raman silent.
● It is not expected to appear in either of the spectrum.
The character table tells us whether the vibrational modes
are IR active and/or Raman active
Symmetry cannot tell us the energies of these modes,
IR Active
where they are going to appear in the spectrum and
● IR active means that it can absorb infrared radiation and
whether some of the modes might overlap because they
cause a molecular vibration in response to it.
have the same energy.
● To be IR active (allowed), the vibration must change the
dipole moment of the molecule.
● We may be interested in the vibrations of specific
○ You can have an oscillating dipole that is
groups in a molecule rather than all possible motions of
driven by the electromagnetic field.
the molecule.
○ Only irreducible representations with x,y,z
symmetry do this.
● Looking at the C-O stretch, we can tell a lot of information
about the molecule and distinguish one isomer from
another.
● In this case, we can create reducible representations of
the bond vectors of interest, determine their irreducible
components, and find the active modes.

Example: Can we use IR/Raman spectroscopy to distinguish


between fac-ML3(CO)3 and mer-ML3(CO)3 isomers?

5 infrared active vibrational modes

Raman Active
● Facial - the three carbonyls are on the same face or the
● To be Raman active (allowed), the vibration must change
same triangular face of the octahedron.
the polarizability of the molecule.
● Meridional - the three carbonyls are along the meridian or
○ Only irreducible representations that
along the equator of the octahedron.
transform like the binary products of x,y,
● Assign the point groups and generate the reducible
and z (i.e. xy, xz, yz, x2, y2, z2 or their linear
representations to do all of the calculations needed.
combinations) do this.
○ Mostly listed in the quadratic column of the
character table.

● Create reducible representations of the C-O bonds in each


molecule
○ Draw in the axis of interest.
INORGANIC CHEMISTRY - FINALS
fac isomer ● C2 - one of the C-O does not change as it is the axis of
rotation, but it changes the other two. (Answer: 1)
● σv (xz) - consider the plane that contains all of the C-O
bonds. None of them change. (Answer: 3).
● σv (yz) - one of the C-O does not change as it is the axis of
reflection, but it flips the other two. (Answer: 1)

Character Table
● E - all three bonds are unchanged (Answer: 3)
● 2C3 - all of the bonds are changed (Answer: 0) Reduce to irreducible representations:
● 3σv - only one of the three bonds are changed while the
other bounce through the plane going to the back.

1
#IRR = 𝑜𝑟𝑑𝑒𝑟
Σ[(# 𝑜𝑝𝑒𝑟𝑎𝑡𝑖𝑜𝑛)(𝑔𝑖𝑣𝑒𝑛)(𝑐ℎ𝑎𝑟𝑎𝑐𝑡𝑒𝑟 𝑡𝑎𝑏𝑙𝑒)]

Reduce to irreducible representations:

1
#IRR = 𝑜𝑟𝑑𝑒𝑟
Σ[(# 𝑜𝑝𝑒𝑟𝑎𝑡𝑖𝑜𝑛)(𝑔𝑖𝑣𝑒𝑛)(𝑐ℎ𝑎𝑟𝑎𝑐𝑡𝑒𝑟 𝑡𝑎𝑏𝑙𝑒)] Assign the number of Infrared and Raman vibrations to the 2A1
and B1

● The mer isomer is expected to have 3 peaks in both its IR


and Raman spectra.

*E is worth 2 based on the character table SUMMARY:


● Group theory can tell us which molecules are chiral,
Assign the number of Infrared and Raman vibrations to the A1 possess dipole moments, possess chemically identical
and E groups, and other symmetry related properties.
● We can use group theory to determine the vibrational
modes of molecules. Procedure:
○ Determine the point group of the molecule.
○ Determine reducible representation for
vectors of interest.
● The fac isomer is expected to have 2 peaks in both its IR ○ Reduce this representation to its irreducible
and Raman spectra components (modes).
mer Isomer ○ If desired, assign the modes to the different
motions (rotations, translations, stretches,
bends, wags, twists, etc.)
○ If desired, read off which modes are
IR/Raman active.

Character Table
● E - all three bonds are unchanged (Answer: 3)
INORGANIC CHEMISTRY - FINALS
YOUTUBE
● When an intense beam of light is passed through a liquid
or gas, some of the light is scattered through the
molecules of the medium.

● The sharp line in the middle corresponds to Rayleigh


scattered light and is referred to as Rayleigh line.
● Ramman scattered light records a series of lines on
either side of the Rayleigh line. These are called Raman
lines and constitute the Raman spectrum.

● Most of the scattered light has the same frequency as the


incident light. This type of scattering which occurs without
a change in the incident frequency is termed Rayleigh
scattering.

● In 1928, Indian physicist Sir


C.V. Raman discovered that a
very small fraction of the
scattered light has
Energy Scheme for Photon Scattering
frequencies higher or lower
than the incident frequency.
● The scattering which occurs
with a change in the
frequency of the incident
radiation is called Raman
scattering. The phenomenon
is called the Raman effect.

● The spectrum obtained from scattered radiations of a


sample can be observed with the help of the apparatus ● The change in frequency by scattering occurs due to the
illustrated: exchange of energy between the incident photon and the
scattering molecule.
● If the photon collides with an ‘excited’ molecule, it
acquires energy from the molecule. Thus the scattered
light emerges with a higher frequency.

● Laser beam is now used as incident radiation. Raman


originally used ultraviolet light which gave weak spectral
lines.
● The general pattern of spectrum recorded by scattered ● If the photon collides with a molecule in the ground state, it
light is illustrated: loses energy to the molecule. This lowers the frequency
of the scattered light.
INORGANIC CHEMISTRY - FINALS
QUESTIONS: RAMAN SPECTROSCOPY
1. Raman effect is a scattering of…
A. Atoms
B. Molecules
C. Protons
D. Photons

2. Raman effect involves (a) scattering of a photon by a


molecule that is raised to (b) energy level.
A. (a) Compton (b) higher
B. (a) X-ray (b) lower
Explanation of Raman Spectra C. (a) Elastic (b) higher
● It explains why the Raman spectrum of a substance D. (a) Inelastic (b) higher
shows lines of higher frequency and others of lower
frequency than the incident line. 3. What type of scattering is it if the frequency of the scattered
● Raman Frequency (VRaman) - The frequency difference radiation is ______ from the frequency of the incident
(∆V) between each Raman line and the incident line. radiation?
● Raman Frequencies shown by a substance are A. Same
independent of the incident frequency and are B. Different
characteristic of the substance.
4. In Raman Spectroscopy, the radiation lies in the ______
A. X-ray region
B. Visible region
C. UV region
D. Microwave region

5. The change in frequency is due to the transition between


vibrational and rotational energy levels.
A. False
B. True

Raman Spectra and Molecular Structure 6. Raman spectrum consists of Stokes lines when the change
● Raman spectra provide valuable information about the in frequency (∆V) is…
shape and structure of molecules. A. > 0
● When studies together, Raman and IR spectra can tell B. Does not depend on ∆V
us whether: C. = 0
1. A molecule is linear or nonlinear.; D. < 0
2. A molecule is symmetrical or asymmetrical.
● The most important application of Raman spectra is in the
determination of structure of organic molecules.

7. Why are the Raman Frequencies the characteristic of the


substance?
● Definite frequencies are associated with different types of ● A Raman frequency is known to be a characteristic of a
bonds. The Raman frequency for: substance because it is able to provide information about
○ C-H bond is about 2800 cm-1, the substance in terms of its shape and structure. It can
○ C≡C bond about 2100 cm-1 determine the presence of different bonds present in its
○ C=C bond about 1600 cm-1. structure based on the difference of the Raman line from
● Thus like infrared spectra; Raman spectra are useful in the incident line.
establishing the structure of organic molecules.
INORGANIC CHEMISTRY - FINALS
Vibrational Spectroscopy: IR vs. Raman Example: Methane (CH3)
Absorption Spectroscopy Scissoring
● When a molecule absorbs radion, it is excited to a higher
energy level.
○ Excitation by microwave or Infrared -
Rotational Transition
○ Infrared or Visible Light - Vibrational
Transition
○ UV-Light - Electronic Transition

Vibrational Spectroscopy: Raman and IR Spectroscopy


● Transition of vibrational states.
● Measure vibrational energy levels associated with a
specific chemical bond.
Rocking
● Uses chemical bonds as Springs derived from Hooke’s
Law. An input of energy causes the molecules to vibrate.

F = -kx

● Molecules have vibrational modes dependent on the


orientation, bonds, mass, bond order, and hydrogen
bonding of the atoms.

● Nonlinear molecules:
3N-6 possible vibrational modes
Infrared Spectroscopy
● Linear molecules: ● More common than Raman Spectroscopy.
3N-5 possible vibrational modes ● Involves irradiating the substance of interest with infrared
light.
● The patterns of vibrations relate to the symmetry of the ● Molecules selectively absorb the energies of the light
molecule, deduce the molecular shape and information corresponding to particular molecular vibrations.
about the strength of each bond.

Example: CO2
Symmetric Stretch

Asymmetric Stretch

IR Instrumentation

● The IR instrument detects the change in absorption


intensity as a function of frequency.
Bend ● Plots amount of light transmitted or absorbed versus
energy and wave numbers.

Transmittance:
(T) = P/P0

P0 - original irradiance of the beam


P - irridance after the beam passes through the sample
INORGANIC CHEMISTRY - FINALS
IR Spectra No Change in Dipole Moment
● Symmetric stretching would not appear because both
oxygen are moving away from the carbon, canceling the
net dipole.

● The greater the change in the dipole moment, the larger


● Absorption bands - peaks in IR spectrum
the peak in the spectrum.
Quantitative Analysis
CO2 IR Spectrum
● IR spectroscopy absorbance is used rather than
● A peak at 2345 cm-1 was observed for the asymmetric
transmittance.
stretch of CO2.
● Another peak at 546 cm-1 for the bend vibrational mode.
Absorption (A): -log T

● Beer’s Law shows how the intensities of absorption bands


and IR are linearly proportional to the concentration of
each component in a system.

A = εbc
● ε - Molar absorptivity ; characteristic of a substance that
tells how much light is absorbed at a particular
wavelength.
● Absorbance is directly proportional to the concentration
of the absorbing reagent.
● A symmetric stretch is predicted at 1537 cm-1 , but it is not
Change in Dipole Moment IR active, resulting in no peaks.
● In order for a molecule to be IR active, there must be a
change in the electric dipole moment of a molecule. Raman Spectroscopy
● The peaks tend to show for polar bonds and ● Not as common as IR spectroscopy, but still provides
non-symmetric vibrations. valuable information about molecular symmetry.
● Sample is radiated with Visible light which the molecule
Example: CO2 absorbs and re-emits.
● Some of the energy is absorbed by the molecular
vibrations causing a small portion to re-emit at a different
frequency than the incident light.
● Light can be scattered in two ways:
○ Elastically (Rayleigh Scattering) - no
non-kinetic transfer between the molecule
and photons.
○ Inelastically (Raman Scattering) - transfer
● The asymmetric stretching would produce a peak in the IR
of energy between molecule and photon.
spectrum.
● Modern Raman spectroscopy instruments are designed to
○ One oxygen moves away from the carbon
filter out the Rayleigh light because only one in every
atom and generates a net charge in dipole
million photons will be Raman scattered.
moments.
● Can be used with an aqueous solutions
● Change in polarizability
INORGANIC CHEMISTRY - FINALS
Raman Intensity vs. Frequency ● This change occurs in symmetric stretching, but not in
● Raman Spectrum - plot of the intensity of the Raman asymmetric stretching.
scattered radiation as a function of its energy difference ● Raman Active vibrational modes:
from the incident radiation (a.k.a Raman Shift). ○ Scissor Stretch
○ Rocking Stretch
○ Symmetric Stretch

● The Asymmetric stretch at 790 cm-1 is barely visible, but


results in a dipole change and will be absorbed in IR
spectroscopy.

COMPARISON:
● Molecules have some vibrational states that can only be
detected in Raman or some that can only be detected in
IR.
● This is due to the method’s dependence on a change in
dipole moment, or change in polarizability.
IR Spectroscopy Raman Spectroscopy
Shifts
● Relatively inexpensive. ● More expensive.
● In Raman scattering, the inelastically scattered light is lost
or gained energy. ● Cannot be used with ● Able to use in aqueous
aqueous solutions. solutions.
○ Use of water
● Change in dipole because water is a
moment. low symmetry
molecule.
● Elaborate sample prep
● Change in polarizability.

● Molecules can be used


in almost any state
making it relatively
simple to prepare.

● Stoke Shift - when the scattered light has lost energy.


● Anti-Stoke Shift - when the scattered light has gained
energy.
● Rayleigh Shift - occurs when there is no overall net
transfer of energy.

CCl4 Spectra
● In order for a molecule to be Raman active, it must have a
change in its polarizability. There must be a change in the
size, shape, or orientation of the electron cloud that
surrounds the molecules.
INORGANIC CHEMISTRY - FINALS
QUESTION: VIBRATIONAL SPECTROSCOPY and IR b. Measures relative frequencies at which a
SPECTROSCOPY sample scatters radiation, unlike IR
1. What kind of transition will result upon visible light spectroscopy which measures absolute
excitation? frequencies at which a sample absorbs
a. Electronic radiation.
b. Rotation c. All of these are correct.
c. Nuclear d. Change in polarizability of a molecule.
d. Vibrational
8. For symmetrical molecules with a center of inversion,
2. The water molecule will have how many vibrational Raman and IR are mutually exclusive. In other words,
peaks? bonds that are IR-active will not be Raman-active and vice
a. 4 versa. This statement is TRUE or FALSE?
b. 2 ● True. For symmetrical molecules with a center of
c. 3 inversion, Raman and IR are mutually exclusive. In
d. 9 other words, bonds that are IR-active will not be
Raman-active and vice versa. Other molecules may
3. Absorption bands associated with C=O bond stretching have bonds that are either Raman-active, IR-active,
frequencies are… neither or both.
a. Are weak because the molecule’s symmetry
b. Usually very strong because a large chain 9. Raman scattering occurs in two ways:
in the dipole takes place in that molecule a. If the emitted radiation is of lower frequency
c. Usually stronger than bending than the incident radiation, then it is called
frequencies Stokes scattering.
d. None of these b. If it is of higher frequency, then it is called
4. The statement “energy of molecular vibration is quantized anti-Stokes scattering.
rather than continuous: c. Stoke shift involves the scattered light losing
a. None of these energy; Anti-Stoke shift when it gains energy
b. Is true meaning that a molecule can only d. All of these are true.
stretch and bend at certain ‘allowed’
frequencies.
c. Is true for simpler molecules
d. Is False

5. If a molecule is exposed to electromagnetic radiation that


matches the frequency of one of its vibrational modes….
a. The difference in energy between the two
vibrational states is equal to the energy
associated with the wavelength of radiation
that was absorbed.
b. it will in most cases absorb energy from the
radiation and jump to a higher vibrational
energy state
c. This means that the amplitude of the
vibration will increase, but the vibrational
frequency will remain the same.
d. All are correct

6. In the IR spectra of CO2…


a. The symmetric stretch is IR-inactive while
the asymmetric stretch does result in a
change in dipole moment so it is IR-active.
b. The symmetric stretch does not result in a
change (of the initially zero dipole moment
c. All of these are correct
d. Carbon dioxide has 4 vibrations expected

7. Raman Spectroscopy
a. Change in the wavelength of light that occurs
when a light beam is deflected by molecules.
INORGANIC CHEMISTRY - FINALS
Explain Stokes and Anti-Stokes Line?
● When a molecular sample is placed in an intense beam of
monochromatic radiations, it transmits the entire incident
light.
● In this case, the molecule gets excited and immediately
returns to the ground state.
● The returning molecule takes place with the emission of
light in all the directions.
● This type of scattering of light is known as Rayleigh
scattering.

https://www.youtube.com/watch?v=JQwRbiqnU3A

You might also like