Point Group
Point Group
Point Group
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.
Ag Ag Au
● 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.
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.
Answer: 2 - 4 = -2
Answer: 0
Answer: 12 - 6 = 6
Answer: 4 - 2 = 0
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
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.
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)]
1
#IRR = 𝑜𝑟𝑑𝑒𝑟
Σ[(# 𝑜𝑝𝑒𝑟𝑎𝑡𝑖𝑜𝑛)(𝑔𝑖𝑣𝑒𝑛)(𝑐ℎ𝑎𝑟𝑎𝑐𝑡𝑒𝑟 𝑡𝑎𝑏𝑙𝑒)] Assign the number of Infrared and Raman vibrations to the 2A1
and B1
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.
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.
F = -kx
● 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
Transmittance:
(T) = P/P0
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
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.
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
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