CHEM 2102 | Introduction to Group Theory Character Tables Associated with each point group is a character table It displays

ys all the symmetry elements of the point group with a description of how various objects or mathematical functions transform under the corresponding symmetry operations Entries in the main part of the table are called characters, , which shows how an object or mathematical function is affected by the corresponding symmetry operation of the group Character 1 1 0 Significance The orbital is unchanged The orbital changes sign The orbital undergoes a more complicated change

The class of an operation is a specific grouping of symmetry operations of the same geometrical type. All operations of the same class have the same character Each row of characters corresponds to a particular irreducible representation of the group The label in the first column is the symmetry species of that irreducible representation (irrep) The group order, h, is the total no of symmetry operations that can be carried out in the point group
Symmetry operations R arranged by class (E, Cn, etc) Order of group, h

Point group (Schoenflies symbol)

Functions Translations and components of dipole moments (x, y, z), of relevance to IR activity, rotations

Further functions

Symmetry species ()

Characters ()

Quadratic functions 2 such as z , xy, etc., of relevance to Raman activity

From character table, pz spans a1 in C2v, px spans b1 in C2v and py spans b2 in C2v The letter A refers to an irrep which is symmetrical with respect to rotation about the two-fold axis, i.e. the character is 1 under the principal rotation The letter B refers to an irrep where the character changes sign under the principal rotation, i.e. the character is -1 The subscript 1 on A1 means that the irrep is symmetrical under reflection in the principal mirror plane The subscript 2 is used when the reflection in the principal mirror plane is antisymmetrical (changes sign) There are other symmetry species labels which indicate degenerate irreps: E always denotes double degneracy (vs E identity) and T denotes triple degeneracy (cf crystal field theory eg and t2g) Degenerate irreps can contain zero values for some operations, which arise because the sum of characters for the degenerate function is zero

Group Theory and Chemical Bonding MO Theory An MO arises from interactions between AOs. In MO theory, assume that the wavefunction of the electrons in a molecule can be written as a product of oneelectron wavefunctions Linear Combination of Atomic Orbitals (LCAO) involves constructing a reasonable approximation of a MO by combining the AOs contributed by each atom in the bond In-phase combination enhanced probability in internuclear region construcive interference bonding orbital Out-of-phase combination nodal plane in internuclear region destructive interference antibonding orbital In general, a MO arises from interactions between the orbitals on AOs. Such interactions are: Allowed if the AOs span the same irrep of the point group (i.e. have the same symmetry) overlap of orbitals (size and symmetry required for bond formation) Efficient if there is significant spatial overlap of the orbitals

Efficient if the AOs are relatively close in energy Example: If the s orbital on 1 atom ( symmetry) combines with a p orbital ( symmetry), the region of constructive interference is cancelled from the region of destructive interference (i.e. no net gain in bonding; no bond is formed) Note: The no of MO formed must equal to the no of AOs on the constituent atoms In describing MOs of polyatomic molecules, the Ligand Group Orbital (LGO) approach is used H 2O

Example

For O 2s orbital, irrep spanned by O2s orbital is A1, label 2s AO on O atom in H2O as a1. Similarly, O2px spans B1, O2py spans B2 and O2pz spans A1 E 1 2 C2 1 0 v (xz) 1 2 v (yz) 1 0

O 2s H 1s

For irreps spanned by H 1s AOs, they swap positions under the principal rotation (0) but are 2 objects (individual species hence 2) Thus, H are not an irrep in C2v. The sum of characters of the A1 and B1 irreps equals the characters found for H1s AO The 2 LGOs must have a1 and b1 symmetries or more correctly, H = (1 x A1) + (0 x A2) + (1 x B1) + (0 x B2)

SALCs Are combinations of AOs that conform to the symmetry of a molecule and are used to construct MOs of a given symmetry species Constructing MOs the labels for MOs are lowercase versions of the symmetry species of the orbital

1. Assign a point group to the molecule 2. Look up the shapes of the SALCs 3. Arrange the SALCs of each molecular fragment in increasing order, first noting whether they stem from s, p, d orbitals (and put them in the order s < p < d), and then their no of internuclear nodes

4. Combine SALCs of the same symmetry type from the 2 fragments, and from N SALCs form N MOs 5. Estimate the relative energies of the MOs from considerations of overlap and relative energies of the parent orbitals, and draw the levels on a MO diagram

Reduction Formula A reducible representation can be resolved into its constituent irreducible representations by using the reduction formula The symbol denotes the symmetry species of the reducible representation

ni =

1 g(R) i (R) (R) h R

where ni = no of times an irrep i appears in the reducible representation R = a symmetry class h = group order (top RHS of character table) g(R) = no of symmetry operations in symmetry class R (read from character table) i(R) = character of symmetry class R for irrep i (read from character table) (R) = character of the reducible representation under the symmetry class R (read from characters of our reducible basis)

nA1 = ((1 x 1 x 2) + (1 x 1 x 0) + (1 x 1 x 2) + (1 x 1 x 0) = (4) = 1 nA2 = ((1 x 1 x 2) + (1 x 1 x 0) + (1 x -1 x 2) + (1 x -1 x 0) = (0) = 0 nB1 = (4) = 1 nB2 = (0) = 0 Thus, the 2 LGOs formed from the H 1s AOs in H2O span a1 and b1 in C2v Note: when applying the reduction formula, the values for ni must be integers, if not theres an error Each of the 2s and 2pz orbitals on the O atom possess the correct symmetry (a1) to interact with the a1 LGO of H. These interactions must lead to 3 MOs (2 bonding MOs (a1) and 1 antibonding (a1*) The interaction between 2px (b1) and H (b1) leads to 2 MOs which possess bonding and antibonding character The oxygen 2py orbital has b2 symmetry and there is no symmetry match with H and is therefore non-bonding in H2O

This gives rise to 4 occupied MOs: 3 bonding and 1 non-bonding. The antibonding orbitals are empty, with electronic configuration: (a1)2 (b1)2 (a1)2 (b2)2 To determine what the 2 H LGO combinations correspond to, look at the effect of each symmetry operation on one of our basis functions under symmetry operations in C2v projection operator method

Projection Operator Method Used to generate SALCs from a basis of orbitals

a = a (i) pi ( )
i

where a = combination of basis functions that gives an orbital of irrep a (symmetry adapted linear combination SALC) a(i) = character of symmetry operation i for irrep a pi() = projection operator of one of the basis functions under symmetry operation i Since the 2 LGOs formed from the 2 H 1s AOs span a1 and b1, a1 = N((1 x 1) + (1 x 2) + (1 x 1) + (1 x 2)) = N (21 + 22) = N (1 + 2) b1 = N((1 x 1) (1 x 2) + (1 x 1) (1 x 2)) = N (21 22) = N (1 2) The a1 SALC is an in-phase combination of H 1s AOs and b1 SALC is an out-ofphase combination

Example

NH3

NH3 has C3v symmetry and a bonding scheme can be derived by considering the interaction between the AOs of the N atom and LGOs of an appropriate H fragment N lies on the point of the point group (centre of symmetry of the molecule) and the irrep spanned by N 2p orbital can be read directly from the character table Hence, N 2px and 2py span E, N 2s and 2pz span A1 For H 1s AO, need to determine irrep spanned by H 1s LGO combinations using the reduction formula Consider how many H 1s orbitals are left unmoved by each symmetry operation in C3v E 3 C3 0 3 v 1

nA1 = 1/6 ((1 x 1 x 3) + (2 x 1 x 0) + (3 x 1 x 1)) = 1 nA2 = 1/6 ((1 x 1 x 3) + (2 x 1 x 0) + (3 x -1 x 1)) = 0 nE = 1/6 ((1 x 2 x 3) + (2 x -1 x 0) + (3 x 0 x 1)) = 1 Hence, the H 1s LGOs span a1 and e in C3v. If we sum up the columns of E and 2C3 and 3v, it turns out to be equal to the H of 3, 0 and 1 (as above) respectively Note: The e here represents double degeneracy of the 2 H orbitals involved, and the other H orbital spans a1

To visualise what the a1 and e H 1s LGOs look like, we use the projection operator to visualise the SALCs

Let the 3 H 1s AOs be 1, 2 and 3 E 1 2 3 C3 2 3 1 C 32 3 1 2 v 1 3 2 v 2 1 3 v 3 2 1

p1 p 2 p 3
a1

= N((1 x 1) + (1 x 2) + (1 x 3) + (1 x 1) + (1 x 2) + (1 x 3)) = N (21 + 22 + 23) = N (1 + 2 + 3) (in-phase combination)

e = N((2 x 1) + (-1 x 2) + (-1 x 3)) = N (21 2 3) However, e is doubly degenerate and must be orthogonal (at right angles) so there must be a second solution. i.e. Choose a second basis function and look at the projection operator for that ( p 2 ) e (LGO2) = N ((2 x 2) + (-1 x 3) + (-1 x 1)) = N (22 3 1)

e (LGO3) = N (23 1 2)

(still not orthogonal to initial solution)

Hence, consider the original SALC the condition for orthogonality means the nodal plane must pass through 1. Hence 1 = 0 in the second e LGO Need to combine other solutions to provide one in which 1 = 0, find that a linear combination of 2 of the solutions gives us an acceptable answer

e = N ((22 3 1) (23 1 2)) = N (32 33) = N (2 3)

Example

Bonding of an octahedral molecule MH6, where M = first row TM

Metal has 4s, 4p and 3d orbitals available for bonding. The H atoms have only 1s AOs and can only form bonds to the metal

The irreps spanned by the TM AOs can be read directly from the Oh character table Hence, the 4s orbital spans a1g, 4px, y and z span t1u Note: The letter g means that the orbital does not change sign under inversion while the letter u means that the orbital changes sign under inversion The metal 3dx2-y2 and 3dz2 span eg while 3dxy, 3dxz and 3dyz span t2g Use the reduction formula to determine the irreps spanned by H 1s combinations by counting the no of unmoved basis functions under each symmetry operation in the Oh point group E 6 C3 0 C2 0 C4 2 C2 2 i 0 S4 0 S6 0 h 4 d 2

H6

Hence, the H 1s LGOs span a1g, eg and t1u Visualise the H 1s SALCs by using the projection operator method

Vibrational Spectroscopy Concerned with the observation of the degrees of vibrational freedom in a molecule The motion of a molecule can be described in terms of 3 degrees of freedom relating to the 3 Cartesian axes, therefore a suitable basis for understanding the possible motions of a H2O molecule is based on atom-centred Cartesian coordinates If a molecule has N atoms, it must have 3N degrees of freedom, which together describe the translational, vibrational and rotational motions of the molecule To understand these displacements, we need to determine irreps spanned in C2v for the basis of atom centred Cartesian coordinates Determine the no of unmoved basis functions under each symmetry operation Note: since each atom can move along +x, +y and +z, we must take into account the sign of the displacement coordinate i.e. if a symmetry operation turns +x into x, count -1) E 9 C2 -1 v (xz) 1 v (yz) 3

disp

Under C2, the H atoms swap and all coordinates are moved and counted zero. For the O atom, Oz to Oz (1), Oy to Oy (-1), Ox to Ox (-1)

Total no of unmoved basis functions under C2 = 0 + 1 1 1 = -1 Under v (xz), all coordinates on the H atom are moved (0). For the O atom, Oz to Oz, Ox to Ox and Oy to Oy Total = 0 + 1 + 1 1 = +1 Under v (yz), since the molecule lies on the yz plane, the effect of symmetry on all atoms is z to z (1 for each atom), y to y (1 for each atom) and x to x (-1 for each atom) Total = (1 x 3) + (1 x 3) + (-1 x 3) = 3

Reduction Formula disp = 3A1 + A2 + 2B1 + 3B2 (span 9 degrees of freedom) The translation of a molecule (i.e. movement through space) can be described in terms of 3 degrees of freedom relating to the Cartesian axes. If all 3 atoms move along +x, the molecule will translate in the x direction Therefore, 3 of the total degrees of freedom must be translations, which can be read directly from the character table for x, y and z functions (A1 in z direction, B2 in y direction and B1 in x direction) trans = A1 + B1 + B2 If there are a total of 3n degrees of freedom and 3 translational modes, there must be 3n 3 degrees of freedom for rotational and vibrational modes. For a non-linear molecule, there are 3 degrees of rotational freedom The irreps spanned by rotations can be read directly from the character table (functions Rx, Ry and Rz) rot = A2 + B1 + B2 For a non-linear molecule, there are only 2 degrees of rotational freedom as rotation about the molecular axis leaves the molecule unchanged The no of degrees of vibrational motion (stretches and bends) in H2O are: 9 (total) 3 (translational) 3 (rotational) = 3 No of degrees of vibrational freedom for a non-linear molecule = 3n 6 and for a linear molecule = 3n 5 By subtraction of trans and rot from disp, vibra = 2A1 + B2 = stretch + bend

Can work out which of these vibrations are stretches by reconsidering the problem in a basis suitable for describing stretching vibrations only Define a basis of 2 vectors oriented along the OH bonds. To determine the irreps spanned by the basis functions, determine the no of unmoved basis functions: E 2 C2 0 v (xz) 0 v (yz) 2

stretch

Using the reduction formula, it is found that stretch span A1 and B2 vib = 2A1 + B2 and stretch = A1 + B2 so bend = A1 by subtraction Use the projection operator to visualise what these stretches look like. Pick a basis function (i.e. r1 vector) and work out / project the effect of each symmetry operation in C2v on r1 E r1 C2 r2 v (xz) r2 v (yz) r1

pr1

A1 = N((1 x r1) + (1 x r2) + (1 x r2) + (1 x r1)) = N(2r1 + 2r2) = N (r1 + r2) in-phase stretching

B2 = N(r1 r2)

out of phase stretching

The bending A1 vibration is one in which the bond angle increases and then decreases (scissoring stretching) Total 3 possible vibrational modes of H2O

An IR or Raman spectrum records the frequency of a molecular vibration, but not all modes of vibration of a particular molecule are observable in both IR and Raman spectra. In any form of spectroscopy, the intensity I of a transition from an initial state (i) to a final state (f) is given by:

I iT f d
Where T = transition state moment operator and d = integration over all space

Infrared Spectroscopy Absorption of radiation by molecules occur only if the charge distributions in i and f differ in a manner corresponding to an electric dipole A transition between i and f is called an electric dipole transition and T is known as the electric dipole moment operator () Group theory can tell us if I is zero or non-zero and to do this, we need to know the irreps spanned by i, f and All molecules will be in their ground vibrational state at room temperature and the ground vibrational state spans the totally symmetric irrep of its point group (i.e. the A1 irrep) - i spans A1 f spans the irreps determined by a group theory analysis of the molecular vibrations (i.e. the irreps spanned by vib) spans the same irreps as the Cartesian x, y and z axes (i.e. these can be read directly from the character table one dimensional functions) The requirement for non-zero intensity (I) is that f spans the same irrep as at least 1 component of (i.e. x, y or z). For H2O, vibra spans 2A1 + B2 so f spans 2A1 + B2 In C2v, spans A1 (z), B1 (x), B2 (y). Therefore, all 3 vibrations of H2O should be visible in its spectrum as they span the same irrep as a component of and all 3 vibrations feature a change in dipole moment

Raman Spectroscopy For a molecular vibration to be detectable, there must be a change in the polarisability of the molecule between the initial state i and final state f

I i f d
Where = polarisability moment operator, spans the same irreps as the quadratic functions in the character table (2 dimensional functions) For H2O, at least 1 component of spans every irrep in C2v and hence, all vibrations of H2O appear in the Raman spectrum

Mutual Exclusion Rule States that any molecule with a centre of inversion (i) cannot have vibrations which appear in both its infrared and Raman spectrum (i.e. only either or)