Solid harmonics: Difference between revisions
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In [[mathematics]], '''solid harmonics''' are defined as solutions of the [[Laplace equation]] in [[spherical polar coordinates]]. There are two kinds of solid harmonic functions: the ''regular solid harmonics'' <math>\scriptstyle R^m_\ell(\mathbf{r})</math>, which vanish at the origin, and the ''irregular solid harmonics'' <math>\scriptstyle I^m_{\ell}(\mathbf{r})</math>, which have an <font style = "vertical-align: top"><math> r^{-(\ell+1)}</math></font> singularity at the origin. Both sets of functions play an important role in [[potential theory]]. Regular solid harmonics appear in [[chemistry]] in the form of ''s'', ''p'', ''d'', etc. [[electron orbital|atomic orbitals]] and in [[physics]] as [[multipoles]]. Irregular harmonics appear in the expansion of scalar fields in terms of multipoles. | |||
Both kinds of solid harmonics are simply related to [[spherical harmonics]] <math>\scriptstyle Y^m_\ell</math> (normalized to unity), | |||
:<math> | |||
R^m_{\ell}(\mathbf{r}) \equiv \sqrt{\frac{4\pi}{2\ell+1}}\; r^\ell Y^m_{\ell}(\theta,\varphi), | |||
\qquad | |||
I^m_{\ell}(\mathbf{r}) \equiv \sqrt{\frac{4\pi}{2\ell+1}} \; \frac{ Y^m_{\ell}(\theta,\varphi)}{r^{\ell+1}} . | |||
</math> | |||
== Derivation, relation to spherical harmonics == | == Derivation, relation to spherical harmonics == | ||
The following vector operator plays a central role in this section | |||
:<math> | :<math> | ||
\mathbf{L} \equiv \mathbf{r} \times \mathbf{\nabla}. | |||
</math> | </math> | ||
where ' | Parenthetically, we remark that in quantum mechanics <math>\scriptstyle -i\hbar \mathbf{L}</math> is the [[Angular momentum (quantum)#Orbital_angular_momentum|orbital angular momentum operator]], where <math>\scriptstyle \hbar\,</math> is [[Planck's constant]] divided by 2π. In quantum mechanics the momentum operator is proportional to the gradient, <math>\scriptstyle \mathbf{p}= -i\hbar\mathbf{\nabla}</math>, so that '''L''' is proportional to '''r'''×'''p''', the orbital [[angular momentum]] operator. | ||
:<math> \mathbf{L} = - | |||
By using the relations | |||
:<math> | |||
L^2 \equiv \mathbf{L}\cdot\mathbf{L} = \sum_{i,j} [r_i\nabla_j r_i \nabla_j - r_i\nabla_j r_j \nabla_i]\quad \hbox{and}\quad \nabla_j r_i - r_i\nabla_j = \delta_{ji} | |||
</math> | |||
one can derive that | |||
:<math> | |||
L^2 = | |||
r^2 \nabla^2 - (\mathbf{r}\cdot\mathbf{\nabla} )^2 - \mathbf{r}\cdot\mathbf{\nabla}. | |||
</math> | |||
Expression in spherical polar coordinates gives: | |||
:<math> | |||
\mathbf{r}\cdot \mathbf{\nabla} = r\frac{\partial}{\partial r} | |||
</math> | |||
and | |||
:<math> | |||
(\mathbf{r}\cdot\mathbf{\nabla} )^2 + \mathbf{r}\cdot\mathbf{\nabla} = | |||
\frac{1}{r} \frac{\partial^2}{\partial r^2} r . | |||
</math> | |||
It can be shown by expression of '''L''' in spherical polar coordinates that L² does not contain a derivative with respect to ''r''. Hence upon division of L² by ''r''² the position of 1/''r''² in the resulting expression is irrelevant. | |||
After these preliminaries we find that the Laplace equation ∇² Φ = 0 can be written as | |||
:<math> | |||
\nabla^2\Phi(\mathbf{r}) = \left(\frac{1}{r} \frac{\partial^2}{\partial r^2}r + \frac{L^2}{r^2} \right)\Phi(\mathbf{r}) = 0 , \qquad \mathbf{r} \ne \mathbf{0}. | |||
</math> | </math> | ||
It is [[Angular momentum#Relation to spherical harmonics|known]] that [[spherical harmonics]] Y<sup>m</sup><sub>l</sub> are eigenfunctions of | It is [[Angular momentum#Relation to spherical harmonics|known]] that [[spherical harmonics]] Y<sup>m</sup><sub>l</sub> are eigenfunctions of L²: | ||
:<math> | :<math> | ||
L^2 Y^m_{\ell} | L^2 Y^m_{\ell} = -\ell(\ell+1) Y^m_{\ell}. | ||
</math> | </math> | ||
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:<math> | :<math> | ||
\frac{1}{r}\frac{\partial^2}{\partial r^2}r F(r) = \frac{\ell(\ell+1)}{r^2} F(r) | \frac{1}{r}\frac{\partial^2}{\partial r^2}r F(r) =\frac{\ell(\ell+1)}{r^2} F(r) | ||
\Longrightarrow F(r) = A r^\ell + B r^{-\ell-1}. | \Longrightarrow F(r) = A r^\ell + B r^{-\ell-1}. | ||
</math> | </math> | ||
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</math> | </math> | ||
(and analogously for the irregular solid harmonic) instead of normalization to unity. This is convenient because in many applications the Racah normalization factor appears unchanged throughout the derivations. | (and analogously for the irregular solid harmonic) instead of normalization to unity. This is convenient because in many applications the Racah normalization factor appears unchanged throughout the derivations. | ||
==Connection between regular and irregular solid harmonics== | |||
From the definitions follows immediately that | |||
:<math> | |||
I^m_\ell(\mathbf{r})= \frac{R^m_{\ell}(\mathbf{r})}{r^{2\ell+1}} | |||
</math> | |||
A more interesting relationship follows from the observation that the regular solid harmonics are [[homogeneous polynomials]] in the components ''x'', ''y'', and ''z'' of '''r'''. We can replace these components by the corresponding components of the gradient operator ∇. Thus, the left hand side in the following equation is well-defined: | |||
:<math> | |||
R^m_\ell(\mathbf{\nabla})\; \frac{1}{r} = (-1)^\ell \frac{(2\ell)!}{2^\ell \ell!}\;I^m_\ell(\mathbf{r}), \qquad r\ne 0. | |||
</math> | |||
For a proof see Biedenharn and Louck (1981), p. 312. | |||
<!-- | |||
<ref>L. C. Biedenharn and J. D. Louck, ''Angular Momentum in Quantum Physics'', volume 8 of Encyclopedia of Mathematics, Addison-Wesley, Reading (1981)</ref>. | |||
--> | |||
==Addition theorems== | ==Addition theorems== | ||
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</math> | </math> | ||
where the [[Clebsch-Gordan coefficient]] is given by | where the [[Clebsch-Gordan coefficient]] is given by | ||
<!-- | |||
:<math> | :<math> | ||
\langle \lambda, \mu; \ell-\lambda, m-\mu| \ell m \rangle | \langle \lambda, \mu; \ell-\lambda, m-\mu| \ell m \rangle | ||
= \binom{\ell+m}{\lambda+\mu}^{1/2} \binom{\ell-m}{\lambda-\mu}^{1/2} \binom{2\ell}{2\lambda}^{-1/2}. | = \binom{\ell+m}{\lambda+\mu}^{1/2} \binom{\ell-m}{\lambda-\mu}^{1/2} \binom{2\ell}{2\lambda}^{-1/2}. | ||
</math> | |||
--> | |||
:<math> | |||
\langle \lambda, \mu; \ell-\lambda, m-\mu| \ell m \rangle | |||
= {\ell+m \choose \lambda+\mu}^{1/2} {\ell-m \choose \lambda-\mu}^{1/2} {2\ell \choose 2\lambda}^{-1/2}. | |||
</math> | </math> | ||
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</math> | </math> | ||
with <math> |r| \le |a|\,</math>. The quantity between pointed brackets is again a [[Clebsch-Gordan coefficient]], | with <math> |r| \le |a|\,</math>. The quantity between pointed brackets is again a [[Clebsch-Gordan coefficient]], | ||
<!-- | |||
:<math> | :<math> | ||
\langle \lambda, \mu; \ell+\lambda, m-\mu| \ell m \rangle | \langle \lambda, \mu; \ell+\lambda, m-\mu| \ell m \rangle | ||
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\binom{2\ell+2\lambda+1}{2\lambda}^{-1/2}. | \binom{2\ell+2\lambda+1}{2\lambda}^{-1/2}. | ||
</math> | </math> | ||
--> | |||
:<math> | |||
\langle \lambda, \mu; \ell+\lambda, m-\mu| \ell m \rangle | |||
= (-1)^{\lambda+\mu}{\ell+\lambda-m+\mu \choose \lambda+\mu}^{1/2} {\ell+\lambda+m-\mu \choose \lambda-\mu}^{1/2}{2\ell+2\lambda+1\choose 2\lambda}^{-1/2}. | |||
</math> | |||
==Real form== | ==Real form== | ||
By a simple linear combination of solid harmonics of ±''m'' these functions are transformed into real functions. The real regular solid harmonics, expressed in | By a simple linear combination of solid harmonics of ±''m'' these functions are transformed into real functions. The real regular solid harmonics, expressed in Cartesian coordinates, are homogeneous polynomials of order ''l'' in ''x'', ''y'', ''z''. The explicit form of these polynomials is of some importance. They appear, for example, in the form of spherical [[atomic orbital]]s and real [[multipole moments]]. The explicit Cartesian expression of the real regular harmonics will now be derived. | ||
====Linear combination ==== | ====Linear combination ==== | ||
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</math> | </math> | ||
Further | Further | ||
<!-- | |||
:<math> | |||
A_m(x,y) \equiv | |||
\frac{1}{2} \left[ (x+iy)^m + (x-iy)^m \right]= \sum_{p=0}^m \binom{m}{p} x^p y^{m-p} \cos\left( (m-p) \frac{\pi}{2}\right) | |||
</math> | |||
--> | |||
:<math> | :<math> | ||
A_m(x,y) \equiv | A_m(x,y) \equiv | ||
\frac{1}{2} \left[ (x+iy)^m + (x-iy)^m \right]= \sum_{p=0}^m | \frac{1}{2} \left[ (x+iy)^m + (x-iy)^m \right]= \sum_{p=0}^m {m\choose p} x^p y^{m-p} \cos\left( (m-p) \frac{\pi}{2} \right) | ||
</math> | </math> | ||
and | and | ||
<!-- | |||
:<math> | |||
B_m(x,y) \equiv | |||
\frac{1}{2i} \left[ (x+iy)^m - (x-iy)^m \right]= \sum_{p=0}^m \binom{m}{p} x^p y^{m-p} \sin\left( (m-p) \frac{\pi}{2}\right). | |||
</math> | |||
--> | |||
:<math> | :<math> | ||
B_m(x,y) \equiv | B_m(x,y) \equiv | ||
\frac{1}{2i} \left[ (x+iy)^m - (x-iy)^m \right]= \sum_{p=0}^m | \frac{1}{2i} \left[ (x+iy)^m - (x-iy)^m \right]= \sum_{p=0}^m {m\choose p} x^p y^{m-p} \sin\left( (m-p) \frac{\pi}{2}\right). | ||
</math> | </math> | ||
====In total ==== | ====In total ==== | ||
:<math> | :<math> | ||
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</math> | </math> | ||
---- | ---- | ||
:<math> | :<math> | ||
\begin{matrix} | |||
\bar{\Pi}^0_0 & | \bar{\Pi}^0_0 = & 1 & | ||
\bar{\Pi}^1_3 & | \bar{\Pi}^1_3 = & \frac{1}{4}\sqrt{6}(5z^2-r^2) & | ||
\bar{\Pi}^4_4 & | \bar{\Pi}^4_4 = & \frac{1}{8}\sqrt{35} \\ | ||
\bar{\Pi}^0_1 & | \bar{\Pi}^0_1 = & z & | ||
\bar{\Pi}^2_3 & | \bar{\Pi}^2_3 = & \frac{1}{2}\sqrt{15}\; z & | ||
\bar{\Pi}^0_5 & | \bar{\Pi}^0_5 = & \frac{1}{8}z(63z^4-70z^2r^2+15r^4) \\ | ||
\bar{\Pi}^1_1 & | \bar{\Pi}^1_1 = & 1 & | ||
\bar{\Pi}^3_3 & | \bar{\Pi}^3_3 = & \frac{1}{4}\sqrt{10} & | ||
\bar{\Pi}^1_5 & | \bar{\Pi}^1_5 = & \frac{1}{8}\sqrt{15} (21z^4-14z^2r^2+r^4) \\ | ||
\bar{\Pi}^0_2 & | \bar{\Pi}^0_2 = & \frac{1}{2}(3z^2-r^2) & | ||
\bar{\Pi}^0_4 & | \bar{\Pi}^0_4 = & \frac{1}{8}(35 z^4-30 r^2 z^2 +3r^4 ) & | ||
\bar{\Pi}^2_5 & | \bar{\Pi}^2_5 = & \frac{1}{4}\sqrt{105}(3z^2-r^2)z \\ | ||
\bar{\Pi}^1_2 & | \bar{\Pi}^1_2 = & \sqrt{3}z & | ||
\bar{\Pi}^1_4 & | \bar{\Pi}^1_4 = & \frac{\sqrt{10}}{4} z(7z^2-3r^2) & | ||
\bar{\Pi}^3_5 & | \bar{\Pi}^3_5 = & \frac{1}{16}\sqrt{70} (9z^2-r^2) \\ | ||
\bar{\Pi}^2_2 & | \bar{\Pi}^2_2 = & \frac{1}{2}\sqrt{3} & | ||
\bar{\Pi}^2_4 & | \bar{\Pi}^2_4 = & \frac{1}{4}\sqrt{5}(7z^2-r^2) & | ||
\bar{\Pi}^4_5 & | \bar{\Pi}^4_5 = & \frac{3}{8}\sqrt{35} z \\ | ||
\bar{\Pi}^0_3 & | \bar{\Pi}^0_3 = & \frac{1}{2} z(5z^2-3r^2) & | ||
\bar{\Pi}^3_4 & | \bar{\Pi}^3_4 = & \frac{1}{4}\sqrt{70}\;z & | ||
\bar{\Pi}^5_5 & | \bar{\Pi}^5_5 = & \frac{3}{16}\sqrt{14} \\ | ||
\end{matrix} | |||
</math> | </math> | ||
---- | ---- | ||
The lowest functions <math>A_m(x,y)\,</math> and <math> B_m(x,y)\,</math> are: | The lowest functions <math>A_m(x,y)\,</math> and <math> B_m(x,y)\,</math> are: | ||
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Thus, for example, the angular part of one of the nine normalized spherical ''g'' [[atomic orbitals]] is: | Thus, for example, the angular part of one of the nine normalized spherical ''g'' [[atomic orbitals]] is: | ||
:<math> | :<math> | ||
C^2_4(x,y,z) = \sqrt{\frac{9}{4\pi}} \sqrt{\frac{5}{16}} (7z^2-r^2)(x^2-y^2). | C^2_4(x,y,z) = \sqrt{{\textstyle\frac{9}{4\pi}}}\bar{\Pi}^2_4 A_2= \sqrt{{\textstyle\frac{9}{4\pi}}} \sqrt{\textstyle{\frac{5}{16}}} (7z^2-r^2)(x^2-y^2). | ||
</math> | </math> | ||
One of the 7 components of a real [[multipole]] of order 3 (octupole) of a system of ''N'' charges ''q''<sub>''i''</sub> is | One of the 7 components of a real [[multipole]] of order 3 (octupole) of a system of ''N'' charges ''q''<sub> ''i''</sub> is | ||
:<math> | :<math> | ||
S^1_3(x,y,z) = \frac{1}{4}\sqrt{6}\sum_{i=1}^N q_i (5z_i^2-r_i^2) y_i . | S^1_3(x,y,z) = \bar{\Pi}^1_3 B_1= \frac{1}{4}\sqrt{6}\sum_{i=1}^N q_i (5z_i^2-r_i^2) y_i . | ||
</math> | </math> | ||
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\end{pmatrix} | \end{pmatrix} | ||
= | = | ||
\left[\frac{2\ell+1}{4\pi}\right]^{1/2} \bar{\Pi}^m_\ell | \left[\frac{2\ell+1}{4\pi}\right]^{1/2} \bar{\Pi}^m_\ell(z) | ||
\begin{pmatrix} | \begin{pmatrix} | ||
(-1)^m (A_m + i B_m)/\sqrt{2} \\ | (-1)^m (A_m + i B_m)/\sqrt{2} \\ | ||
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:<math> | :<math> | ||
r^\ell\,Y_\ell^{0} \equiv \sqrt{\frac{2\ell+1}{4\pi}} | r^\ell\,Y_\ell^{0} \equiv \sqrt{\frac{2\ell+1}{4\pi}} | ||
\bar{\Pi}^0_\ell . | \bar{\Pi}^0_\ell(z) . | ||
</math> | </math> | ||
Here | Here | ||
<!-- | |||
:<math> | |||
A_m(x,y) = \sum_{p=0}^m \binom{m}{p} x^p y^{m-p} \cos\left( (m-p) \frac{\pi}{2}\right), | |||
</math> | |||
--> | |||
:<math> | :<math> | ||
A_m(x,y) = \sum_{p=0}^m | A_m(x,y) = \sum_{p=0}^m {m \choose p} x^p y^{m-p} \cos\left( (m-p) \frac{\pi}{2}\right), | ||
</math> | </math> | ||
<!-- | |||
:<math> | |||
B_m(x,y) = \sum_{p=0}^m \binom{m}{p} x^p y^{m-p} \sin (m-p)\left( \frac{\pi}{2}\right), | |||
</math> | |||
--> | |||
:<math> | :<math> | ||
B_m(x,y) = \sum_{p=0}^m | B_m(x,y) = \sum_{p=0}^m {m\choose p} x^p y^{m-p} \sin\left( (m-p) \frac{\pi}{2} \right), | ||
</math> | </math> | ||
and for ''m'' > 0: | and for ''m'' > 0: | ||
<!-- | |||
:<math> | :<math> | ||
\bar{\Pi}^m_\ell(z) | \bar{\Pi}^m_\ell(z) | ||
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\sum_{k=0}^{\left \lfloor (\ell-m)/2\right \rfloor} | \sum_{k=0}^{\left \lfloor (\ell-m)/2\right \rfloor} | ||
(-1)^k 2^{-\ell} \binom{\ell}{k}\binom{2\ell-2k}{\ell} \frac{(\ell-2k)!}{(\ell-2k-m)!} | (-1)^k 2^{-\ell} \binom{\ell}{k}\binom{2\ell-2k}{\ell} \frac{(\ell-2k)!}{(\ell-2k-m)!} | ||
\; r^{2k}\; z^{\ell-2k-m}. | |||
</math> | |||
--> | |||
:<math> | |||
\bar{\Pi}^m_\ell(z) | |||
= \left[\frac{(\ell-m)!}{(\ell+m)!}\right]^{1/2} | |||
\sum_{k=0}^{\left \lfloor (\ell-m)/2\right \rfloor} | |||
(-1)^k 2^{-\ell} {\ell\choose k}{2\ell-2k \choose \ell} \frac{(\ell-2k)!}{(\ell-2k-m)!} | |||
\; r^{2k}\; z^{\ell-2k-m}. | \; r^{2k}\; z^{\ell-2k-m}. | ||
</math> | </math> | ||
For ''m'' = 0: | For ''m'' = 0: | ||
<!-- | |||
:<math> | :<math> | ||
\bar{\Pi}^0_\ell(z) | \bar{\Pi}^0_\ell(z) | ||
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(-1)^k 2^{-\ell} \binom{\ell}{k}\binom{2\ell-2k}{\ell} \; r^{2k}\; z^{\ell-2k}. | (-1)^k 2^{-\ell} \binom{\ell}{k}\binom{2\ell-2k}{\ell} \; r^{2k}\; z^{\ell-2k}. | ||
</math> | </math> | ||
--> | |||
:<math> | |||
\bar{\Pi}^0_\ell(z) | |||
= \sum_{k=0}^{\left \lfloor \ell/2\right \rfloor} | |||
(-1)^k 2^{-\ell} {\ell \choose k}{2\ell-2k \choose \ell} \; r^{2k}\; z^{\ell-2k}. | |||
</math> | |||
=====Examples===== | =====Examples===== | ||
Using the expressions for <math>\bar{\Pi}^\ell_m(z)</math>, <math>A_m(x,y)\,</math>, and <math>B_m(x,y)\,</math> listed explicitly above we obtain: | Using the expressions for <math>\bar{\Pi}^\ell_m(z)</math>, <math>A_m(x,y)\,</math>, and <math>B_m(x,y)\,</math> listed explicitly above we obtain: | ||
:<math> | :<math> | ||
Y^1_3 = - \frac{1}{r^3} \left[\ | Y^1_3 = - \frac{1}{r^3} \left[{\textstyle \frac{7}{4\pi}\cdot \frac{3}{16} }\right]^{1/2} (5z^2-r^2)(x+iy) = | ||
- \left[\ | - \left[{\textstyle \frac{7}{4\pi}\cdot \frac{3}{16}}\right]^{1/2} (5\cos^2\theta-1) (\sin\theta e^{i\varphi}) | ||
</math> | </math> | ||
:<math> | :<math> | ||
Y^{-2}_4 = \frac{1}{r^4} \left[\ | Y^{-2}_4 = \frac{1}{r^4} \left[{\textstyle \frac{9}{4\pi}\cdot\frac{5}{32}}\right]^{1/2}(7z^2-r^2) (x-iy)^2 | ||
= \left[\ | = \left[{\textstyle \frac{9}{4\pi}\cdot\frac{5}{32}}\right]^{1/2}(7 \cos^2\theta -1) (\sin^2\theta e^{-2 i \varphi}) | ||
</math> | </math> | ||
==References== | |||
Most books on angular momenta discuss solid harmonics. See, for instance, | |||
* D. M. Brink and G. R. Satchler, ''Angular Momentum'', 3rd edition ,Clarendon, Oxford, (1993) | |||
* L. C. Biedenharn and J. D. Louck, ''Angular Momentum in Quantum Physics'', volume 8 of Encyclopedia of Mathematics, Addison-Wesley, Reading (1981) | |||
The addition theorems for solid harmonics have been proved in different manners by many different workers. See for two different proofs for example: | |||
* R. J. A. Tough and A. J. Stone, J. Phys. A: Math. Gen. Vol. '''10''', p. 1261 (1977) | |||
* M. J. Caola, J. Phys. A: Math. Gen. Vol. '''11''', p. L23 (1978)[[Category:Suggestion Bot Tag]] |
Latest revision as of 06:00, 20 October 2024
In mathematics, solid harmonics are defined as solutions of the Laplace equation in spherical polar coordinates. There are two kinds of solid harmonic functions: the regular solid harmonics Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \scriptstyle R^m_\ell(\mathbf{r})} , which vanish at the origin, and the irregular solid harmonics Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \scriptstyle I^m_{\ell}(\mathbf{r})} , which have an Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle r^{-(\ell+1)}} singularity at the origin. Both sets of functions play an important role in potential theory. Regular solid harmonics appear in chemistry in the form of s, p, d, etc. atomic orbitals and in physics as multipoles. Irregular harmonics appear in the expansion of scalar fields in terms of multipoles.
Both kinds of solid harmonics are simply related to spherical harmonics Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \scriptstyle Y^m_\ell} (normalized to unity),
- Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle R^m_{\ell}(\mathbf{r}) \equiv \sqrt{\frac{4\pi}{2\ell+1}}\; r^\ell Y^m_{\ell}(\theta,\varphi), \qquad I^m_{\ell}(\mathbf{r}) \equiv \sqrt{\frac{4\pi}{2\ell+1}} \; \frac{ Y^m_{\ell}(\theta,\varphi)}{r^{\ell+1}} . }
Derivation, relation to spherical harmonics
The following vector operator plays a central role in this section
- Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \mathbf{L} \equiv \mathbf{r} \times \mathbf{\nabla}. }
Parenthetically, we remark that in quantum mechanics Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \scriptstyle -i\hbar \mathbf{L}} is the orbital angular momentum operator, where Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \scriptstyle \hbar\,} is Planck's constant divided by 2π. In quantum mechanics the momentum operator is proportional to the gradient, Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \scriptstyle \mathbf{p}= -i\hbar\mathbf{\nabla}} , so that L is proportional to r×p, the orbital angular momentum operator.
By using the relations
- Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle L^2 \equiv \mathbf{L}\cdot\mathbf{L} = \sum_{i,j} [r_i\nabla_j r_i \nabla_j - r_i\nabla_j r_j \nabla_i]\quad \hbox{and}\quad \nabla_j r_i - r_i\nabla_j = \delta_{ji} }
one can derive that
- Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle L^2 = r^2 \nabla^2 - (\mathbf{r}\cdot\mathbf{\nabla} )^2 - \mathbf{r}\cdot\mathbf{\nabla}. }
Expression in spherical polar coordinates gives:
- Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \mathbf{r}\cdot \mathbf{\nabla} = r\frac{\partial}{\partial r} }
and
- Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle (\mathbf{r}\cdot\mathbf{\nabla} )^2 + \mathbf{r}\cdot\mathbf{\nabla} = \frac{1}{r} \frac{\partial^2}{\partial r^2} r . }
It can be shown by expression of L in spherical polar coordinates that L² does not contain a derivative with respect to r. Hence upon division of L² by r² the position of 1/r² in the resulting expression is irrelevant. After these preliminaries we find that the Laplace equation ∇² Φ = 0 can be written as
- Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \nabla^2\Phi(\mathbf{r}) = \left(\frac{1}{r} \frac{\partial^2}{\partial r^2}r + \frac{L^2}{r^2} \right)\Phi(\mathbf{r}) = 0 , \qquad \mathbf{r} \ne \mathbf{0}. }
It is known that spherical harmonics Yml are eigenfunctions of L²:
- Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle L^2 Y^m_{\ell} = -\ell(\ell+1) Y^m_{\ell}. }
Substitution of Φ(r) = F(r) Yml into the Laplace equation gives, after dividing out the spherical harmonic function, the following radial equation and its general solution,
- Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \frac{1}{r}\frac{\partial^2}{\partial r^2}r F(r) =\frac{\ell(\ell+1)}{r^2} F(r) \Longrightarrow F(r) = A r^\ell + B r^{-\ell-1}. }
The particular solutions of the total Laplace equation are regular solid harmonics:
- Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle R^m_{\ell}(\mathbf{r}) \equiv \sqrt{\frac{4\pi}{2\ell+1}}\; r^\ell Y^m_{\ell}(\theta,\varphi), }
and irregular solid harmonics:
- Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle I^m_{\ell}(\mathbf{r}) \equiv \sqrt{\frac{4\pi}{2\ell+1}} \; \frac{ Y^m_{\ell}(\theta,\varphi)}{r^{\ell+1}} . }
Racah's normalization (also known as Schmidt's semi-normalization) is applied to both functions
- Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \int_{0}^{\pi}\sin\theta\, d\theta \int_0^{2\pi} d\varphi\; R^m_{\ell}(\mathbf{r})^*\; R^m_{\ell}(\mathbf{r}) = \frac{4\pi}{2\ell+1} r^{2\ell} }
(and analogously for the irregular solid harmonic) instead of normalization to unity. This is convenient because in many applications the Racah normalization factor appears unchanged throughout the derivations.
Connection between regular and irregular solid harmonics
From the definitions follows immediately that
- Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle I^m_\ell(\mathbf{r})= \frac{R^m_{\ell}(\mathbf{r})}{r^{2\ell+1}} }
A more interesting relationship follows from the observation that the regular solid harmonics are homogeneous polynomials in the components x, y, and z of r. We can replace these components by the corresponding components of the gradient operator ∇. Thus, the left hand side in the following equation is well-defined:
- Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle R^m_\ell(\mathbf{\nabla})\; \frac{1}{r} = (-1)^\ell \frac{(2\ell)!}{2^\ell \ell!}\;I^m_\ell(\mathbf{r}), \qquad r\ne 0. }
For a proof see Biedenharn and Louck (1981), p. 312.
Addition theorems
The translation of the regular solid harmonic gives a finite expansion,
- Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle R^m_\ell(\mathbf{r}+\mathbf{a}) = \sum_{\lambda=0}^\ell\binom{2\ell}{2\lambda}^{1/2} \sum_{\mu=-\lambda}^\lambda R^\mu_{\lambda}(\mathbf{r}) R^{m-\mu}_{\ell-\lambda}(\mathbf{a})\; \langle \lambda, \mu; \ell-\lambda, m-\mu| \ell m \rangle, }
where the Clebsch-Gordan coefficient is given by
- Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \langle \lambda, \mu; \ell-\lambda, m-\mu| \ell m \rangle = {\ell+m \choose \lambda+\mu}^{1/2} {\ell-m \choose \lambda-\mu}^{1/2} {2\ell \choose 2\lambda}^{-1/2}. }
The similar expansion for irregular solid harmonics gives an infinite series,
- Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle I^m_\ell(\mathbf{r}+\mathbf{a}) = \sum_{\lambda=0}^\infty\binom{2\ell+2\lambda+1}{2\lambda}^{1/2} \sum_{\mu=-\lambda}^\lambda R^\mu_{\lambda}(\mathbf{r}) I^{m-\mu}_{\ell+\lambda}(\mathbf{a})\; \langle \lambda, \mu; \ell+\lambda, m-\mu| \ell m \rangle }
with Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle |r| \le |a|\,} . The quantity between pointed brackets is again a Clebsch-Gordan coefficient,
- Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \langle \lambda, \mu; \ell+\lambda, m-\mu| \ell m \rangle = (-1)^{\lambda+\mu}{\ell+\lambda-m+\mu \choose \lambda+\mu}^{1/2} {\ell+\lambda+m-\mu \choose \lambda-\mu}^{1/2}{2\ell+2\lambda+1\choose 2\lambda}^{-1/2}. }
Real form
By a simple linear combination of solid harmonics of ±m these functions are transformed into real functions. The real regular solid harmonics, expressed in Cartesian coordinates, are homogeneous polynomials of order l in x, y, z. The explicit form of these polynomials is of some importance. They appear, for example, in the form of spherical atomic orbitals and real multipole moments. The explicit Cartesian expression of the real regular harmonics will now be derived.
Linear combination
We write in agreement with the earlier definition
- Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle R_\ell^m(r,\theta,\varphi) = (-1)^{(m+|m|)/2}\; r^\ell \;\Theta_{\ell}^{|m|} (\cos\theta) e^{im\varphi}, \qquad -\ell \le m \le \ell, }
with
- Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \Theta_{\ell}^m (\cos\theta) \equiv \left[\frac{(\ell-m)!}{(\ell+m)!}\right]^{1/2} \,\sin^m\theta\, \frac{d^m P_\ell(\cos\theta)}{d\cos^m\theta}, \qquad m\ge 0, }
where Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle P_\ell(\cos\theta)} is a Legendre polynomial of order l. The m dependent phase is known as the Condon-Shortley phase.
The following expression defines the real regular solid harmonics:
- Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \begin{pmatrix} C_\ell^{m} \\ S_\ell^{m} \end{pmatrix} \equiv \sqrt{2} \; r^\ell \; \Theta^{m}_\ell \begin{pmatrix} \cos m\varphi\\ \sin m\varphi \end{pmatrix} = \frac{1}{\sqrt{2}} \begin{pmatrix} (-1)^m & \quad 1 \\ -(-1)^m i & \quad i \end{pmatrix} \begin{pmatrix} R_\ell^{m} \\ R_\ell^{-m} \end{pmatrix}, \qquad m > 0. }
and for m = 0:
- Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle C_\ell^{0} \equiv R_\ell^{0} . }
Since the transformation is by a unitary matrix the normalization of the real and the complex solid harmonics is the same.
z-dependent part
Upon writing u = cos θ the mth derivative of the Legendre polynomial can be written as the following expansion in u
- Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \frac{d^m P_\ell(u)}{du^m} = \sum_{k=0}^{\left \lfloor (\ell-m)/2\right \rfloor} \gamma^{(m)}_{\ell k}\; u^{\ell-2k-m} }
with
- Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \gamma^{(m)}_{\ell k} = (-1)^k 2^{-\ell} {\ell\choose k}{2\ell-2k \choose \ell} \frac{(\ell-2k)!}{(\ell-2k-m)!}. }
Since z = r cosθ it follows that this derivative, times an appropriate power of r, is a simple polynomial in z,
- Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \Pi^m_\ell(z)\equiv r^{\ell-m} \frac{d^m P_\ell(u)}{du^m} = \sum_{k=0}^{\left \lfloor (\ell-m)/2\right \rfloor} \gamma^{(m)}_{\ell k}\; r^{2k}\; z^{\ell-2k-m}. }
(x,y)-dependent part
Consider next, recalling that x = r sinθcosφ and y = r sinθsinφ,
- Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle r^m \sin^m\theta \cos m\varphi = \frac{1}{2} \left[ (r \sin\theta e^{i\varphi})^m + (r \sin\theta e^{-i\varphi})^m \right] = \frac{1}{2} \left[ (x+iy)^m + (x-iy)^m \right] }
Likewise
- Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle r^m \sin^m\theta \sin m\varphi = \frac{1}{2i} \left[ (r \sin\theta e^{i\varphi})^m - (r \sin\theta e^{-i\varphi})^m \right] = \frac{1}{2i} \left[ (x+iy)^m - (x-iy)^m \right]. }
Further
- Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle A_m(x,y) \equiv \frac{1}{2} \left[ (x+iy)^m + (x-iy)^m \right]= \sum_{p=0}^m {m\choose p} x^p y^{m-p} \cos\left( (m-p) \frac{\pi}{2} \right) }
and
- Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle B_m(x,y) \equiv \frac{1}{2i} \left[ (x+iy)^m - (x-iy)^m \right]= \sum_{p=0}^m {m\choose p} x^p y^{m-p} \sin\left( (m-p) \frac{\pi}{2}\right). }
In total
- Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle C^m_\ell(x,y,z) = \left[\frac{(2-\delta_{m0}) (\ell-m)!}{(\ell+m)!}\right]^{1/2} \Pi^m_{\ell}(z)\;A_m(x,y),\qquad m=0,1, \ldots,\ell }
- Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle S^m_\ell(x,y,z) = \left[\frac{2 (\ell-m)!}{(\ell+m)!}\right]^{1/2} \Pi^m_{\ell}(z)\;B_m(x,y) ,\qquad m=1,2,\ldots,\ell. }
List of lowest functions
We list explicitly the lowest functions up to and including l = 5 . Here Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \bar{\Pi}^m_\ell(z) \equiv \left[\frac{(2-\delta_{m0}) (\ell-m)!}{(\ell+m)!}\right]^{1/2} \Pi^m_{\ell}(z) . }
- Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \begin{matrix} \bar{\Pi}^0_0 = & 1 & \bar{\Pi}^1_3 = & \frac{1}{4}\sqrt{6}(5z^2-r^2) & \bar{\Pi}^4_4 = & \frac{1}{8}\sqrt{35} \\ \bar{\Pi}^0_1 = & z & \bar{\Pi}^2_3 = & \frac{1}{2}\sqrt{15}\; z & \bar{\Pi}^0_5 = & \frac{1}{8}z(63z^4-70z^2r^2+15r^4) \\ \bar{\Pi}^1_1 = & 1 & \bar{\Pi}^3_3 = & \frac{1}{4}\sqrt{10} & \bar{\Pi}^1_5 = & \frac{1}{8}\sqrt{15} (21z^4-14z^2r^2+r^4) \\ \bar{\Pi}^0_2 = & \frac{1}{2}(3z^2-r^2) & \bar{\Pi}^0_4 = & \frac{1}{8}(35 z^4-30 r^2 z^2 +3r^4 ) & \bar{\Pi}^2_5 = & \frac{1}{4}\sqrt{105}(3z^2-r^2)z \\ \bar{\Pi}^1_2 = & \sqrt{3}z & \bar{\Pi}^1_4 = & \frac{\sqrt{10}}{4} z(7z^2-3r^2) & \bar{\Pi}^3_5 = & \frac{1}{16}\sqrt{70} (9z^2-r^2) \\ \bar{\Pi}^2_2 = & \frac{1}{2}\sqrt{3} & \bar{\Pi}^2_4 = & \frac{1}{4}\sqrt{5}(7z^2-r^2) & \bar{\Pi}^4_5 = & \frac{3}{8}\sqrt{35} z \\ \bar{\Pi}^0_3 = & \frac{1}{2} z(5z^2-3r^2) & \bar{\Pi}^3_4 = & \frac{1}{4}\sqrt{70}\;z & \bar{\Pi}^5_5 = & \frac{3}{16}\sqrt{14} \\ \end{matrix} }
The lowest functions Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle A_m(x,y)\,} and Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle B_m(x,y)\,} are:
m Am Bm 0 Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle 1\,} Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle 0\,} 1 Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle x\,} Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle y\,} 2 Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle x^2-y^2\,} Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle 2xy\,} 3 4 5
Examples
Thus, for example, the angular part of one of the nine normalized spherical g atomic orbitals is:
One of the 7 components of a real multipole of order 3 (octupole) of a system of N charges q i is
Spherical harmonics in Cartesian form
The following expresses normalized spherical harmonics in Cartesian coordinates (Condon-Shortley phase):
and for m = 0:
Here
and for m > 0:
For m = 0:
Examples
Using the expressions for , Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle A_m(x,y)\,} , and Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle B_m(x,y)\,} listed explicitly above we obtain:
- Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle Y^1_3 = - \frac{1}{r^3} \left[{\textstyle \frac{7}{4\pi}\cdot \frac{3}{16} }\right]^{1/2} (5z^2-r^2)(x+iy) = - \left[{\textstyle \frac{7}{4\pi}\cdot \frac{3}{16}}\right]^{1/2} (5\cos^2\theta-1) (\sin\theta e^{i\varphi}) }
- Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle Y^{-2}_4 = \frac{1}{r^4} \left[{\textstyle \frac{9}{4\pi}\cdot\frac{5}{32}}\right]^{1/2}(7z^2-r^2) (x-iy)^2 = \left[{\textstyle \frac{9}{4\pi}\cdot\frac{5}{32}}\right]^{1/2}(7 \cos^2\theta -1) (\sin^2\theta e^{-2 i \varphi}) }
References
Most books on angular momenta discuss solid harmonics. See, for instance,
- D. M. Brink and G. R. Satchler, Angular Momentum, 3rd edition ,Clarendon, Oxford, (1993)
- L. C. Biedenharn and J. D. Louck, Angular Momentum in Quantum Physics, volume 8 of Encyclopedia of Mathematics, Addison-Wesley, Reading (1981)
The addition theorems for solid harmonics have been proved in different manners by many different workers. See for two different proofs for example:
- R. J. A. Tough and A. J. Stone, J. Phys. A: Math. Gen. Vol. 10, p. 1261 (1977)
- M. J. Caola, J. Phys. A: Math. Gen. Vol. 11, p. L23 (1978)