Solid harmonics

In physics and mathematics, the solid harmonics are solutions of the Laplace equation in spherical polar coordinates. There are two kinds: the regular solid harmonics ${\displaystyle R_{\ell }^{m}(\mathbf {r} )}$, which vanish at the origin and the irregular solid harmonics ${\displaystyle I_{\ell }^{m}(\mathbf {r} )}$, which are singular at the origin. Both sets of functions play an important role in potential theory, and are obtained by rescaling spherical harmonics appropriately:

${\displaystyle R_{\ell }^{m}(\mathbf {r} )=r^{\ell }Y_{\ell }^{m}(\theta ,\phi ).}$

Introducing r, θ, and φ for the spherical polar coordinates of the 3-vector r, we can write the Laplace equation in the following form

${\displaystyle \nabla ^{2}\Phi (\mathbf {r} )=\left({\frac {1}{r}}{\frac {\partial ^{2}}{\partial r^{2}}}r-{\frac {L^{2}}{\hbar ^{2}r^{2}}}\right)\Phi (\mathbf {r} )=0,\qquad \mathbf {r} \neq \mathbf {0} ,}$

where L² is the square of the angular momentum operator,

${\displaystyle \mathbf {L} =-i\hbar \,(\mathbf {r} \times \mathbf {\nabla } ).}$

It is known that spherical harmonics Y^m_l are eigenfunctions of L²,,

${\displaystyle L^{2}Y_{\ell }^{m}\equiv \left[L_{x}^{2}+L_{y}^{2}+L_{z}^{2}\right]Y_{\ell }^{m}=\ell (\ell +1)Y_{\ell }^{m}.}$

Substitution of Φ(r) = F(r) Y^m_l into the Laplace equation gives, after dividing out the spherical harmonic function, the following radial equation and its general solution,

${\displaystyle {\frac {1}{r}}{\frac {\partial ^{2}}{\partial r^{2}}}rF(r)={\frac {\ell (\ell +1)}{r^{2}}}F(r)\Longrightarrow F(r)=Ar^{\ell }+Br^{-\ell -1}.}$

The particular solutions of the total Laplace equation are regular solid harmonics:

${\displaystyle R_{\ell }^{m}(\mathbf {r} )\equiv {\sqrt {\frac {4\pi }{2\ell +1}}}\;r^{\ell }Y_{\ell }^{m}(\theta ,\varphi ),}$

and irregular solid harmonics:

${\displaystyle I_{\ell }^{m}(\mathbf {r} )\equiv {\sqrt {\frac {4\pi }{2\ell +1}}}\;{\frac {Y_{\ell }^{m}(\theta ,\varphi )}{r^{\ell +1}}}.}$

Racah's normalization (also known as Schmidt's semi-normalization) is applied to both functions

${\displaystyle \int _{0}^{\pi }\sin \theta \,d\theta \int _{0}^{2\pi }d\varphi \;R_{\ell }^{m}(\mathbf {r} )^{*}\;R_{\ell }^{m}(\mathbf {r} )={\frac {4\pi }{2\ell +1}}r^{2\ell }}$

(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.

The translation of the regular solid harmonic gives a finite expansion,

${\displaystyle R_{\ell }^{m}(\mathbf {r} +\mathbf {a} )=\sum _{\lambda =0}^{\ell }{\binom {2\ell }{2\lambda }}^{1/2}\sum _{\mu =-\lambda }^{\lambda }R_{\lambda }^{\mu }(\mathbf {r} )R_{\ell -\lambda }^{m-\mu }(\mathbf {a} )\;\langle \lambda ,\mu ;\ell -\lambda ,m-\mu |\ell m\rangle ,}$

where the Clebsch-Gordan coefficient is given by

${\displaystyle \langle \lambda ,\mu ;\ell -\lambda ,m-\mu |\ell m\rangle ={\binom {\ell +m}{\lambda +\mu }}^{1/2}{\binom {\ell -m}{\lambda -\mu }}^{1/2}{\binom {2\ell }{2\lambda }}^{-1/2}.}$

The similar expansion for irregular solid harmonics gives an infinite series,

${\displaystyle I_{\ell }^{m}(\mathbf {r} +\mathbf {a} )=\sum _{\lambda =0}^{\infty }{\binom {2\ell +2\lambda +1}{2\lambda }}^{1/2}\sum _{\mu =-\lambda }^{\lambda }R_{\lambda }^{\mu }(\mathbf {r} )I_{\ell +\lambda }^{m-\mu }(\mathbf {a} )\;\langle \lambda ,\mu ;\ell +\lambda ,m-\mu |\ell m\rangle }$

with ${\displaystyle |r|\leq |a|\,}$. The quantity between pointed brackets is again a Clebsch-Gordan coefficient,

${\displaystyle \langle \lambda ,\mu ;\ell +\lambda ,m-\mu |\ell m\rangle =(-1)^{\lambda +\mu }{\binom {\ell +\lambda -m+\mu }{\lambda +\mu }}^{1/2}{\binom {\ell +\lambda +m-\mu }{\lambda -\mu }}^{1/2}{\binom {2\ell +2\lambda +1}{2\lambda }}^{-1/2}.}$

The addition theorems were 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)

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.

We write in agreement with the earlier definition

${\displaystyle R_{\ell }^{m}(r,\theta ,\varphi )=(-1)^{(m+|m|)/2}\;r^{\ell }\;\Theta _{\ell }^{|m|}(\cos \theta )e^{im\varphi },\qquad -\ell \leq m\leq \ell ,}$

with

${\displaystyle \Theta _{\ell }^{m}(\cos \theta )\equiv \left[{\frac {(\ell -m)!}{(\ell +m)!}}\right]^{1/2}\,\sin ^{m}\theta \,{\frac {d^{m}P_{\ell }(\cos \theta )}{d\cos ^{m}\theta }},\qquad m\geq 0,}$

where ${\displaystyle P_{\ell }(\cos \theta )}$ 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:

${\displaystyle {\begin{pmatrix}C_{\ell }^{m}\\S_{\ell }^{m}\end{pmatrix}}\equiv {\sqrt {2}}\;r^{\ell }\;\Theta _{\ell }^{m}{\begin{pmatrix}\cos m\varphi \\\sin m\varphi \end{pmatrix}}={\frac {1}{\sqrt {2}}}{\begin{pmatrix}(-1)^{m}&\quad 1\\-(-1)^{m}i&\quad i\end{pmatrix}}{\begin{pmatrix}R_{\ell }^{m}\\R_{\ell }^{-m}\end{pmatrix}},\qquad m>0.}$

and for m = 0:

${\displaystyle C_{\ell }^{0}\equiv R_{\ell }^{0}.}$

Since the transformation is by a unitary matrix the normalization of the real and the complex solid harmonics is the same.

Upon writing u = cos θ the mth derivative of the Legendre polynomial can be written as the following expansion in u

${\displaystyle {\frac {d^{m}P_{\ell }(u)}{du^{m}}}=\sum _{k=0}^{\left\lfloor (\ell -m)/2\right\rfloor }\gamma _{\ell k}^{(m)}\;u^{\ell -2k-m}}$

with

${\displaystyle \gamma _{\ell k}^{(m)}=(-1)^{k}2^{-\ell }{\binom {\ell }{k}}{\binom {2\ell -2k}{\ell }}{\frac {(\ell -2k)!}{(\ell -2k-m)!}}.}$

Since z = r cosθ it follows that this derivative, times an appropriate power of r, is a simple polynomial in z,

${\displaystyle \Pi _{\ell }^{m}(z)\equiv r^{\ell -m}{\frac {d^{m}P_{\ell }(u)}{du^{m}}}=\sum _{k=0}^{\left\lfloor (\ell -m)/2\right\rfloor }\gamma _{\ell k}^{(m)}\;r^{2k}\;z^{\ell -2k-m}.}$

Consider next, recalling that x = r sinθcosφ and y = r sinθsinφ,

${\displaystyle r^{m}\sin ^{m}\theta \cos m\varphi ={\frac {1}{2}}\left[(r\sin \theta e^{i\varphi })^{m}+(r\sin \theta e^{-i\varphi })^{m}\right]={\frac {1}{2}}\left[(x+iy)^{m}+(x-iy)^{m}\right]}$

Likewise

${\displaystyle r^{m}\sin ^{m}\theta \sin m\varphi ={\frac {1}{2i}}\left[(r\sin \theta e^{i\varphi })^{m}-(r\sin \theta e^{-i\varphi })^{m}\right]={\frac {1}{2i}}\left[(x+iy)^{m}-(x-iy)^{m}\right].}$

Further

${\displaystyle A_{m}(x,y)\equiv {\frac {1}{2}}\left[(x+iy)^{m}+(x-iy)^{m}\right]=\sum _{p=0}^{m}{\binom {m}{p}}x^{p}y^{m-p}\cos(m-p){\frac {\pi }{2}}}$

and

${\displaystyle B_{m}(x,y)\equiv {\frac {1}{2i}}\left[(x+iy)^{m}-(x-iy)^{m}\right]=\sum _{p=0}^{m}{\binom {m}{p}}x^{p}y^{m-p}\sin(m-p){\frac {\pi }{2}}.}$

${\displaystyle C_{\ell }^{m}(x,y,z)=\left[{\frac {(2-\delta _{m0})(\ell -m)!}{(\ell +m)!}}\right]^{1/2}\Pi _{\ell }^{m}(z)\;A_{m}(x,y),\qquad m=0,1,\ldots ,\ell }$

${\displaystyle S_{\ell }^{m}(x,y,z)=\left[{\frac {2(\ell -m)!}{(\ell +m)!}}\right]^{1/2}\Pi _{\ell }^{m}(z)\;B_{m}(x,y),\qquad m=1,2,\ldots ,\ell .}$

We list explicitly the lowest functions up to and including l = 5 . Here ${\displaystyle {\bar {\Pi }}_{\ell }^{m}(z)\equiv \left[{\tfrac {(2-\delta _{m0})(\ell -m)!}{(\ell +m)!}}\right]^{1/2}\Pi _{\ell }^{m}(z).}$

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${\displaystyle {\begin{aligned}{\bar {\Pi }}_{0}^{0}&=1&{\bar {\Pi }}_{3}^{1}&={\frac {1}{4}}{\sqrt {6}}(5z^{2}-r^{2})&{\bar {\Pi }}_{4}^{4}&={\frac {1}{8}}{\sqrt {35}}\\{\bar {\Pi }}_{1}^{0}&=z&{\bar {\Pi }}_{3}^{2}&={\frac {1}{2}}{\sqrt {15}}\;z&{\bar {\Pi }}_{5}^{0}&={\frac {1}{8}}z(63z^{4}-70z^{2}r^{2}+15r^{4})\\{\bar {\Pi }}_{1}^{1}&=1&{\bar {\Pi }}_{3}^{3}&={\frac {1}{4}}{\sqrt {10}}&{\bar {\Pi }}_{5}^{1}&={\frac {1}{8}}{\sqrt {15}}(21z^{4}-14z^{2}r^{2}+r^{4})\\{\bar {\Pi }}_{2}^{0}&={\frac {1}{2}}(3z^{2}-r^{2})&{\bar {\Pi }}_{4}^{0}&={\frac {1}{8}}(35z^{4}-30r^{2}z^{2}+3r^{4})&{\bar {\Pi }}_{5}^{2}&={\frac {1}{4}}{\sqrt {105}}(3z^{2}-r^{2})z\\{\bar {\Pi }}_{2}^{1}&={\sqrt {3}}z&{\bar {\Pi }}_{4}^{1}&={\frac {\sqrt {10}}{4}}z(7z^{2}-3r^{2})&{\bar {\Pi }}_{5}^{3}&={\frac {1}{16}}{\sqrt {70}}(9z^{2}-r^{2})\\{\bar {\Pi }}_{2}^{2}&={\frac {1}{2}}{\sqrt {3}}&{\bar {\Pi }}_{4}^{2}&={\frac {1}{4}}{\sqrt {5}}(7z^{2}-r^{2})&{\bar {\Pi }}_{5}^{4}&={\frac {3}{8}}{\sqrt {35}}z\\{\bar {\Pi }}_{3}^{0}&={\frac {1}{2}}z(5z^{2}-3r^{2})&{\bar {\Pi }}_{4}^{3}&={\frac {1}{4}}{\sqrt {70}}\;z&{\bar {\Pi }}_{5}^{5}&={\frac {3}{16}}{\sqrt {14}}\\\end{aligned}}}$

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The lowest functions ${\displaystyle A_{m}(x,y)\,}$ and ${\displaystyle B_{m}(x,y)\,}$ are:

m	Am	Bm
0	${\displaystyle 1\,}$	${\displaystyle 0\,}$
1	${\displaystyle x\,}$	${\displaystyle y\,}$
2	${\displaystyle x^{2}-y^{2}\,}$	${\displaystyle 2xy\,}$
3	${\displaystyle x^{3}-3xy^{2}\,}$	${\displaystyle 3x^{2}y-y^{3}\,}$
4	${\displaystyle x^{4}-6x^{2}y^{2}+y^{4}\,}$	${\displaystyle 4x^{3}y-4xy^{3}\,}$
5	${\displaystyle x^{5}-10x^{3}y^{2}+5xy^{4}\,}$	${\displaystyle 5x^{4}y-10x^{2}y^{3}+y^{5}\,}$

Thus, for example, the angular part of one of the nine normalized spherical g atomic orbitals is:

${\displaystyle C_{4}^{2}(x,y,z)={\sqrt {\frac {9}{4\pi }}}{\sqrt {\frac {5}{16}}}(7z^{2}-r^{2})(x^{2}-y^{2}).}$

One of the 7 components of a real multipole of order 3 (octupole) of a system of N charges q_i is

${\displaystyle S_{3}^{1}(x,y,z)={\frac {1}{4}}{\sqrt {6}}\sum _{i=1}^{N}q_{i}(5z_{i}^{2}-r_{i}^{2})y_{i}.}$

The following expresses normalized spherical harmonics in Cartesian coordinates (Condon-Shortley phase):

${\displaystyle r^{\ell }\,{\begin{pmatrix}Y_{\ell }^{m}\\Y_{\ell }^{-m}\end{pmatrix}}=\left[{\frac {2\ell +1}{4\pi }}\right]^{1/2}{\bar {\Pi }}_{\ell }^{m}(z){\begin{pmatrix}(-1)^{m}(A_{m}+iB_{m})/{\sqrt {2}}\\\qquad (A_{m}-iB_{m})/{\sqrt {2}}\\\end{pmatrix}},\qquad m>0.}$

and for m = 0:

${\displaystyle r^{\ell }\,Y_{\ell }^{0}\equiv {\sqrt {\frac {2\ell +1}{4\pi }}}{\bar {\Pi }}_{\ell }^{0}.}$

Here

${\displaystyle A_{m}(x,y)=\sum _{p=0}^{m}{\binom {m}{p}}x^{p}y^{m-p}\cos((m-p){\frac {\pi }{2}}),}$

${\displaystyle B_{m}(x,y)=\sum _{p=0}^{m}{\binom {m}{p}}x^{p}y^{m-p}\sin((m-p){\frac {\pi }{2}}),}$

and for m > 0:

${\displaystyle {\bar {\Pi }}_{\ell }^{m}(z)=\left[{\frac {(\ell -m)!}{(\ell +m)!}}\right]^{1/2}\sum _{k=0}^{\left\lfloor (\ell -m)/2\right\rfloor }(-1)^{k}2^{-\ell }{\binom {\ell }{k}}{\binom {2\ell -2k}{\ell }}{\frac {(\ell -2k)!}{(\ell -2k-m)!}}\;r^{2k}\;z^{\ell -2k-m}.}$

For m = 0:

${\displaystyle {\bar {\Pi }}_{\ell }^{0}(z)=\sum _{k=0}^{\left\lfloor \ell /2\right\rfloor }(-1)^{k}2^{-\ell }{\binom {\ell }{k}}{\binom {2\ell -2k}{\ell }}\;r^{2k}\;z^{\ell -2k}.}$

Using the expressions for ${\displaystyle {\bar {\Pi }}_{m}^{\ell }(z)}$, ${\displaystyle A_{m}(x,y)\,}$, and ${\displaystyle B_{m}(x,y)\,}$ listed explicitly above we obtain:

${\displaystyle Y_{3}^{1}=-{\frac {1}{r^{3}}}\left[{\tfrac {7}{4\pi }}\cdot {\tfrac {3}{16}}\right]^{1/2}(5z^{2}-r^{2})(x+iy)=-\left[{\tfrac {7}{4\pi }}\cdot {\tfrac {3}{16}}\right]^{1/2}(5\cos ^{2}\theta -1)(\sin \theta e^{i\varphi })}$

${\displaystyle Y_{4}^{-2}={\frac {1}{r^{4}}}\left[{\tfrac {9}{4\pi }}\cdot {\tfrac {5}{32}}\right]^{1/2}(7z^{2}-r^{2})(x-iy)^{2}=\left[{\tfrac {9}{4\pi }}\cdot {\tfrac {5}{32}}\right]^{1/2}(7\cos ^{2}\theta -1)(\sin ^{2}\theta e^{-2i\varphi })}$

It may be verified that this agrees with the function listed here and here.