The hydrogen atoms in a methane molecule \(\mathrm{CH}_{4}\) form a perfect
tetrahedron with the carbon atom at its centre. The molecule is most
conveniently described mathematically by placing the hydrogen atoms at the
points \((1,1,1),(1,-1,-1)\), \((-1,1,-1)\) and \((-1,-1,1) .\) The symmetry group
to which it belongs, the tetrahedral group \(\left(\overline{4} 3 m\right.\) or
\(T_{d}\) ) has classes typified by \(I, 3,2_{z}, m_{d}\) and \(\overline{4}_{z}\),
where the first three are as in exercise \(25.5, m_{d}\) is a reflection in the
mirror plane \(x-y=0\) and \(\overline{4}_{2}\) is a rotation of \(\pi / 2\) about
the \(z\)-axis followed by an inversion in the origin. \(A\) reflection in a
mirror plane can be considered as a rotation of \(\pi\) about an axis
perpendicular to the plane, followed by an inversion in the origin.
The character table for the group \(43 m\) is very similar to that for the group
432, and has the form shown in table \(25.9 .\) By following the steps given
below, determine how many different internal vibration frequencies the
\(\mathrm{CH}_{4}\) molecule has.
(a) Consider a representation based on the 12 coordinates \(x_{i}, y_{i},
z_{l}\) for \(i=\) \(1,2,3,4 .\) For those hydrogen atoms that transform into
themselves, a rotation through an angle \(\theta\) about an axis parallel to one
of the coordinate axes gives rise in the natural representation to the
diagonal elements 1 for the corresponding coordinate and \(2 \cos \theta\) for
the two orthogonal coordinates. If the rotation is followed by an inversion
then these entries are multiplied by -1. Atoms not transforming into
themselves give a zero diagonal contribution. Show that the characters of the
natural representation are \(12,0,0,0,2\) and hence that its expression in terms
of irreps is
$$
\mathrm{A}_{1} \oplus \mathrm{E} \oplus \mathrm{T}_{1} \oplus 2
\mathrm{~T}_{2}
$$
(b) The irreps of the bodily translational and rotational motions are included
in this expression and need to be identified and removed. Show that when this
is done it can be concluded that there are three different internal vibration
frequencies in the \(\mathrm{CH}_{4}\) molecule. State their degeneracies and
check that they are consistent with the expected number of normal coordinates
needed to describe the internal motions of the molecule.