Polar Angle Dependence
−n ≤ m ≤ n, (12.152)
which are orthonormal with respect to the polar angle θ .
Spherical Harmonics
The function m (ϕ ) (Eq. (12.150)) is orthonormal with respect to the azimuthal angle ϕ . We take the product of m (ϕ ) and the orthonormal function in polar angle from Eq. (12.152) and define
to obtain functions of two angles (and two indices) that are orthonormal over the spherical surface. These (θ , ϕ ) are spherical harmonics, of which the first few are plotted in Fig. 12.15. The complete orthogonality integral becomes
The extra (−1)m included in the defining equation of (θ , ϕ ) deserves some comment.
It is clearly legitimate, since Eq. (12.144) is linear and homogeneous. It is not necessary, but in moving on to certain quantum mechanical calculations, particularly in the quantum theory of angular momentum (Section 12.7), it is most convenient. The factor (−1)m is a phase factor, often called the Condon–Shortley phase, after the authors of a classic text on atomic spectroscopy. The effect of this (−1)m (Eq. (12.153)) and the (−1)m of Eq. (12.73c) for (cos θ) is to introduce an alternation of sign among the positive m spherical harmonics. This is shown in Table 12.3.
The functions (θ , ϕ ) acquired the name spherical harmonics first because they are defined over the surface of a sphere with θ the polar angle and ϕ the azimuth. The harmonic was included because solutions of Laplace’s equation were called harmonic functions and (cos,ϕ ) is the angular part of such a solution.
Table 12.3 Spherical Harmonics (Condon–Shortley Phase)
In the framework of quantum mechanics Eq. (12.145) becomes an orbital angular momentum equation and the solution (θ , ϕ ) (n replaced by L, m replaced by M )isan angular momentum eigenfunction, L being the angular momentum quantum number and M the z-axis projection of L.
Laplace Series, Expansion Theorem
Part of the importance of spherical harmonics lies in the completeness property, a consequence of the Sturm–Liouville form of Laplace’s equation. This property, in this case, means that any function f(θ , ϕ ) (with sufficient continuity properties) evaluated over the surface of the sphere can be expanded in a uniformly convergent double series of spherical harmonics (Laplace’s series):
If f(θ , ϕ ) is known, the coefficients can be immediately found by the use of the orthogonality integral.
Table 12.4 Gravity Field Coefficients, Eq. (12.156)
Example : LAPLACE SERIES —GRAVITY FIELDS
The gravity fields of the Earth, the Moon, and Mars have been described by a Laplace series with real eigenfunctions:
ORBITAL ANGULAR MOMENTUM OPERATORS
Now we return to the specific orbital angular momentum operators Lx ,Ly , and Lz of quantum mechanics introduced in Section 4.3. Equation (4.68) becomes
and we want to show that
From L+ ψLL = 0,L being the largest M , using the form of L+ given in Exercises 2.5.14 and 12.6.7, we have
(12.158)
and thus
(12.159)
Normalizing, we obtain
(12.160)
The θ integral may be evaluated as a beta function (Exercise 8.4.9) and
(12.161)
This completes our first step.
Again, note that the relative phases are set by the ladder operators. L+ and L− operating
Repeating these operations n times yields
From Eq. (12.163),
and for M =−L:
Note the characteristic (−1)L phase of ψL,−L relative to ψL,L .This (−1)L enters from
(12.167)
Combining Eqs. (12.163), (12.163), and (12.166), we obtain
Equations (12.165) and (12.168) agree if
(12.169)
Using Rodrigues’ formula, Eq. (12.65), we have
(12.170)
The last equality follows from Eq. (12.161). We now demand that ψL0 (0, 0) be real and positive. Therefore
(12.171)
The expression in the curly bracket is identified as the associated Legendre function (Eq. (12.151), and we have
in complete agreement with Section 12.6. Then by Eq. (12.73c), for negative superscript is given by
(12.174)
THE ADDITION THEOREM FOR SPHERICAL HARMONICS
Trigonometric Identity
In the following discussion, (θ1 ,ϕ1 ) and (θ2 ,ϕ2 ) denote two different directions in our spherical coordinate system (x1 ,y1 ,z1 ), separated by an angle γ (Fig. 12.16). The polar angles θ1 ,θ2 are measured from the z1 -axis. These angles satisfy the trigonometric identity
(12.175)
which is perhaps most easily proved by vector methods
The addition theorem, then, asserts that
or equivalently,
In terms of the associated Legendre functions, the addition theorem is
Equation (12.175) is a special case of Eq. (12.178), n = 1.
Derivation of Addition Theorem
We need for our proof only the coefficient which we get by multiplying Eq. (12.179) by and integrating over the sphere:
(12.180)
Similarly, we expand Pn (cos γ) in terms of spherical harmonics
(12.181)
In terms of spherical harmonics Eq. (12.182) becomes
Note that the subscripts have been dropped from the solid angle element dΩ Since the range of integration is over all solid angles, the choice of polar axis is irrelevant. Then comparing Eqs. (12.180) and (12.183), we see that
(12.184)
Now we evaluate using the expansion of Eq. (12.179) and noting that the values of (γ , ξ ) corresponding to (θ1 ,ϕ1 ) = (θ2 ,ϕ2 ) are (0, 0). The result is
(12.185)
all terms with nonzero σ vanishing. Substituting this back into Eq. (12.184), we obtain
(12.186)
Finally, substituting this expression for bnm into the summation, Eq. (12.181) yields Eq. (12.177), thus proving our addition theorem.
Those familiar with group theory will find a much more elegant proof of Eq. (12.177) by using the rotation group.
One application of the addition theorem is in the construction of a Green’s function for the three-dimensional Laplace equation in spherical polar coordinates. If the source is on
the polar axis at the point (r = a, θ = 0,ϕ = 0), then, by Eq. (12.4a),
(12.187)
Rotating our coordinate system to put the source at (a , θ2 ,ϕ2) and the point of observation at (r, θ1 ,ϕ1), we obtain
Exercises
1. Two protons are uniformly distributed within the same spherical volume. If the coordinates of one element of charge are (r1 ,θ1 ,ϕ1 ) and the coordinates of the other are (r2 ,θ2 ,ϕ2 ) and r12 is the distance between them, the element of energy of repulsion will be given by
Here
Calculate the total electrostatic energy (of repulsion) of the two protons. This calculation is used in accounting for the mass difference in “mirror” nuclei, such as O 15 and N15 .
This is double that required to create a uniformly charged sphere because we have two separate cloud charges interacting, not one charge interacting with itself (with permutation of pairs not considered).
2. Each of the two 1S electrons in helium may be described by a hydrogenic wave function
in the absence of the other electron. Here Z , the atomic number, is 2. The symbol a0 is bthye Bohr radius, h¯ 2 /me2 . Find the mutual potential energy of the two electrons, given
3. The probability of finding a 1 S hydrogen electron in a volume element r 2 dr sin θd θd ϕ is
Find the corresponding electrostatic potential. Calculate the potential from
with r1 not on the z-axis. Expand r12 . Apply the Legendre polynomial addition theorem and show that the angular dependence of V(r1 ) drops out.
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