--%>

Molecular Symmetry Types

The number of molecular orbitals and molecular motions of each symmetry type can be deduced.

Let us continue to use the C2v point group and the H2O molecule to illustrate how the procedure developed in preceding sections can be used to deduce the symmetry of molecular properties.

Bond orbitals to molecular orbitals: suppose that the electrons in one bond of an H2O molecule are described by a bond Ø1 and those in the other bond by Ø2. These bond orbitals can be used to construct molecular orbitals. Each molecular orbital must transform according to one of the symmetry species of the C2v point group, that to which the H2O molecule belongs.

The transformation matrices that describe the effect of the various symmetry operations on the two bond orbitals can be seen.

The characters of the representation provided by these transformation matrices are the sums of the diagonal elements. If we write 1408_Reducible Representation.png to represent the characters, we have

2215_molecular symmetry.png 

According to the deduction these are also the characters that would have been obtained if we had used molecular orbitals as a basis. But the characters for each molecular orbital must be drawn from those for the irreducible representation of the point group.

1408_Reducible Representation.png = 1408_Reducible Representation.png Ai + 1408_Reducible Representation.png Bi

Thus we have discovered that the molecular orbitals, the eigenfunctions for the H2O molecule that are constructed from orbitals along the individual bonds, must be of the symmetry types A1 and B1.

A convenient way to obtain characters: the transformation matrices do not have to be written to obtain the characters 2, 0, 2, 0 shown above. A diagonal element occurs only if the bond is turned into itself or in other cases turned into the opposite of itself. Bonds (or vectors or orbitals) shifted from one to another equivalent atom do not degenerate any diagonal elements. Thus, with for each symmetry operation we write a contribution of +1 for each unshifted bond orbital. The result for E is 2, for C2 is 0, for σv is 2, and for σ'v is 0. These are the same characters as we obtained earlier by working out the transformation matrices.

Translations, rotations and vibrations: now let us see whether we can classify the overall translational and rotational motions and the vibrational motions of the H2O molecule according to symmetry. We begin as in the analysis of the number of degrees of freedom by treating these motions in terms of the three displacement coordinates on each atom. These 3n vectors provide a basis on which the symmetry operation of the C2v group, to which the H2O molecule belongs, can act.

We need not work out the 9 × 9 transformations matrices that describe the effect of EC2σvand σ'v on the nine displacement vectors. We need only deduce the characters i.e. the sum of the diagonal elements, of these matrices.

An entry occurs along the diagonal of a transformation matrix for an atom cannot exchange places with another atom as a result of the symmetry operation. Thus for each exchange places operations effect of each symmetry operation will be to leave each of these vectors unchanged or to reverse them. In the former case a + 1 will be contributed to the diagonal terms; in the latter case a - 1 will be contributed. Inspection of the effect of the symmetry operations on the nine displacement vectors that provide a basis for the translations, rotations, and vibrations of the molecule gives
                
1444_molecular symmetry1.png  

Now, in principle, a change in coordinates could be found such that the nine displacement coordinates would combine to give coordinates for the three translational motions and the three rotational motions of the molecule as a whole and the three vibrational motions of the atoms of the molecule. (Such a transformation was worked through for diatomic molecules.

The transformation matrices that describe the effects of the symmetry operations on these new displacement sets would be different from those describing the effects on the displacement vectors. But the sum of the diagonal elements of these transformation matrices would be unaffected. Thus we can treat the set of numbers 9, -1, 3, 1 as being the net characters for the three translational, three rotational, and three vibrational motions.

We can express the result by writing

1408_Reducible Representation.png = 3 1408_Reducible Representation.png A1 + 1408_Reducible Representation.png A2 + 3 1408_Reducible Representation.png B1 + 2 1408_Reducible Representation.png B2

   Related Questions in Chemistry

  • Q : What are haloalkanes and haloarenes and

    Alkyl halides or haloalkanes are the compounds in which a halogen is bonded to an alkyl group. They have the general formula RX (where R is alkyl grou

  • Q : How can enzymes act as catalyst?

    Enzymes are complex proteinous substances, produced by living bodies, such as act as catalysis in the physiological reactions. The enzymes are, also called biochemical catalysts and the phenomenon is known as bio-chemical catalysis because numerous reactions that occur the bodies of animals and p

  • Q : Q what is the basicity of primary

    what is the basicity of primary secondary and tertiary amines in chlorobenzene

  • Q : What type of bond does HCl encompass

    What type of bond does HCl encompass? Describe briefly?

  • Q : Molal concentration Select the right

    Select the right answer of the question. If one mole of any substance is present in of solvent, then: (a) It shows molar concentration (b) It shows molal concentration (c) It shows normality (d) It shows strength.

  • Q : Anti-aromatic and the non-aromatic

    What is main difference among anti-aromatic and the non-aromatic compounds?

  • Q : Decinormal concentration of Sulfuric

    Give me answer of this question. The volume of water to be added to 100cm3 of 0.5 N N H2SO4 to get decinormal concentration is : (a) 400 cm3 (b) 500cm3 (c) 450cm3 (d)100cm3

  • Q : Benzoic acid is weaker than paranitro

    Briefly state that Benzoic acid is weaker than paranitro benzoic acid?

  • Q : Number of moles present in water

    Provide solution of this question. How many moles of water are present in 180 of water: (a)1 mole (b)18 mole (c)10 mole (d)100 mole

  • Q : Molecular weight of solute Select right

    Select right answer of the question. A dry air is passed through the solution, containing the 10 gm of solute and 90 gm of water and then it pass through pure water. There is the depression in weight of solution wt by 2.5 gm and in weight of pure solvent by 0.05 gm. C