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The Spherical Angular Coordinates

The position of a particle on the surface of a sphere of radius r

is more conveniently determined in terms of two angular
variables or coordinates f and q.

f is called the azimuthal angle and q, is called the zenith

angle.

The angle f is the angle measured in the xy plane between the

x-axis and the projection of the line r joining the partilce (P)
with the centre of the sphere (FIG), it varies from o to 2p.

The angle q is the angle between the line r and the z-axis, it
varies from 0 to p.

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The Schrödinger Equation

Since the particle rotates in three-dimensions the Hamiltonian

in cartesian coordinates, if potential energy V is zero, is

---- (1)

Where x, y and z are the coordinates of the particle at any

point.

However, with the present for of the Hamiltonian, the

Schrödinger equation cannot be solved by the method of
separation of variables as the variables x, y and z do not vary
independently of each other here.

The equation can be solved by transforming equation (1) into

one involving q and f by making use of the relation between
cartesian (x, y, z) and angular (q, f) variables.

x = r sin q cos f, y = r sin q sin f, z = r cos q ---- (2)

The transformation, then, is a straightforward application of the

theory of partial derivatives. (Final Expression added)

---- (3)
Since r is constant,

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---- (4)

The Schrödinger equation, Ĥ y = E y becomes

----(5)
Simplifying,

---- (6)

Where the wave function y is y (q, f)

Separation of Variables

Equation (6) can be solved by separating the variables.

We suppose that the function y (q, f) is a product of two

functions P (q) and F (f), each being a function of a single
variable only. i.e.,

y (q, f) = P(q) F (f) ---- (7)

Differentiating partially w.r.t. q,

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Differentiating w.r.t. f,

Substituting above relations into equation (6)

Multiplying throughout by

P and F stand for P (q) and F (f) respectively.

----(8)
The LHS of equation (8) depends on q only while the RHS
depends on f only

If f is maintained constant while q varies, the RHS will remain

constant

Since LHS = RHS, the LHS will also remain equal to the same
constant even though q varies.

Same argument applies to the situation when q is kept constant

and f varies.

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Both sides of equation (8) are, therefore, equal to the same

constant.

Let the constant be denoted by M2 for convenience. Thus, the

equation (8) splits into two ordinary differential equations

---- (9)

and multiplying equation (8) by

---- (10)

where ---- (11)

The F-Equation

The equation (9) is similar to that for particle in a ring. Solution

of equation:

---- (12)

and ---- (13)

where M is a quantum number which has values 0, ±1, ±2,…..

It differs only in that the eigenvalue here does not contain
energy term E.

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The P-Equation –
Legendre and Associated Legendre Functions

---- (10)

The equation (10) is known as Legendre differential equation.

Working out its solution is lengthy and tedious.
Such equations are solved using polynomial method.

Significant Properties of Solutions

For each value of |M| there will be a corresponding Legendre equation

and a new set of solutions. The symbol | | indicates that only the
magnitude and not the sign of M is to be used.

Well-behaved solutions are obtained only for some discrete value of b.

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Well-behaved solutions are obtained only for some discrete value of

b. We may examine a few cases for this:
Consider firstly, the case of |M| = 0. The Legendre equation is

---- (11)

The solutions to this equation exist as polynomials in cos q, called

“Legendre Polynomials” given below

---- (12)

where x = cos q and l is an integer including 0.

Some of these polynomials alongwith the characteristic values of b

are given in Table

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13

The indices of the functions P correspond to the highest power of

cosq in the polynomial.

It can be seen that b = l (l + 1) ---- (13)

where l = 0, 1, 2, 3
For |M| ≠ 0 the solutions are of the form

---- (14)

The polynomials (14) are called “Associated Legendre Polynomials”

We may work out the functions for some values of |M| and l,
|M| = 0 l=0 P00 (x) = 1 = P0 (x) = 1
l=1 P10 (x) = P1 (x) = ½(2x) = x = cosx
l=2 P20 (x) = P2 (x) = 1/8· d2/dx2 (x2-1)2
= ½ (3x2 -1) = ½ (3cos2 q - 1)

14

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and so on

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Putting cos q for x, we may write the associated Legendre functions

that are solution of equation (10) as

---- (15)

-- (16)

The normalisation factor is

---- (17)

Some of the Legendre functions Pl|M| (cos q) can be tabulated.

The Table shows the functions and their normalisation factors for
various values of |M| and l.

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The associated Legendre function PlM (cos q) are characterised by

two parameters l and M.
The value of M is restricted to 0, ±1, ±2, ±3,….
while that of l can be 0, 1, 2, 3,….

The nature of the functions imposes a restriction on the uppermost

value of M that M ≤ 1, i.e., states with |M| > l cannot exist.

Working out for state with l = 1 and M = +2 we get another fact

For a given value of l, M can be chosen from the set

M = - l, (- l + 1), …. 0, …. (l - 1), + l

l and M are identified with the quantum numbers of energy and

angular momentum

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The Complete Wavefunction (Spherical Harmonics)

The complete wave function of the particle on a sphere (or a rigid

rotator) may now be written

Where N is normalisation factor given by previous equation (17) of

the associated legendre function Pl|M| (cos q) eqn (16).

This function is characterized by two quantum number l and M.

Expressed as trigonometric functions (real form) they represent

harmonic waves on the surface of a sphere and are called “spherical
harmonics

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