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Dipole angular selection rules

Statement

Assume the Axiom of Countable Choice (The Axiom of Countable Choice (ACω)). Use the notation of Harmonic polynomial dimension: S2={x∈R3:∣x∣=1} with polar measure σ (Sphere integrals in angle coordinates, Complex Lp classes and Euclidean test-function conventions), the Hilbert space L2(S2,σ) with inner product linear in the first argument, the complete orthonormal family (Ylm) (Associated Legendre function normalization, Sphere ONB), the blocks Vl=span⁡{Yl,−l,…,Yll} and the finite span H, the spaces Hlpol of complex harmonic homogeneous polynomials of degree l, and the polynomial representatives hlm∈Hlpol of the Ylm, characterized by resl(hlm)=Ylm where resl(p) is the class of p∣S2 (homogeneous polynomial and homogeneous ideal, Monomials, coefficients, degree in each variable and total degree in F[x1,…,xn], The Laplacian of a C2 function and of a C2 vector field). Put H−1pol:={0}, fix l≥0 and m∈{−l,…,l}, write H:=hlm, and define the three polynomial multipliers Q0:=x3,Q±:=x1±ix22, so that Qq=∑i=13cq,ixi with c0,i=δi3 and c±,i=(δi1±i δi2)/2. Let Di and Lz,L3 be as in Orbital self-adjoint generators, where L3=Lz and LzYlm=ℏmYlm (Sphere Laplacian diagonal domain). Then, for each q∈{−1,0,1}:

(a) (harmonic decomposition) the polynomial Gq:=∑icq,i ∂iH2l+1 lies in Hl−1pol and Qq H=Rq+r2Gq,Rq:=QqH−r2Gq∈Hl+1pol, where r2(x)=x12+x22+x32; for l=0 one has Gq=0 and Rq=QqH;

(b) (degree selection) the function Qq∣S2⋅Ylm lies in Vl+1⊕Vl−1 (with V−1:={0}); consequently, for all l′≥0 and m′∈{−l′,…,l′}, ⟨Qq∣S2 Ylm, Yl′m′⟩=0whenever l′∉{l−1, l+1};

(c) (weight selection) as elements of H⊂L2(S2,σ) one has Lz(Qq∣S2 Ylm)=ℏ(m+q) (Qq∣S2 Ylm), because ∂φQq=iq Qq on S2 (Sine and cosine defined by their real power series, The complex exponential by its power series); hence in addition ⟨Qq∣S2 Ylm, Yl′m′⟩=0whenever m′≠m+q;

(d) (selection rules) combining (b) and (c): the angular matrix element ⟨Yl′m′, Qq∣S2 Ylm⟩ can be nonzero only if l′=l+1 and m′=m+q,orl≥1, l′=l−1 and m′=m+q; in particular only Δl=±1 and Δm∈{0,±1} occur with the component-dependent shift Δm=q for the multiplier Qq. These are necessary conditions on the angular integrals only: no assertion is made that an allowed pair has a nonzero integral, and no absorption, emission or transition probability is asserted or computed.

Facts & Assumptions

Given: the family (Ylm) with representatives hlm, the multipliers Qq, the fixed indices l,m, and the polynomial H=hlm.

[F1]

The restriction map resl:Hlpol→Vl is a C-linear isomorphism; (Ylm)m is an orthonormal basis of Vl; Vl⊥Vk for l≠k; (Ylm) is complete in L2(S2,σ) and H is dense (Harmonic polynomial dimension (b),(c), Sphere ONB, Orthonormal families, complete orthonormal systems and Hilbert bases, Parseval equivalences for an orthonormal family, Real and complex inner product spaces, with the inner product linear in the first argument).

[F2]

Δ is linear, satisfies the product rule Δ(fg)=fΔg+2∇f⋅∇g+gΔf, commutes with each ∂i, and annihilates the coordinate functions xi; r2 has Δr2=6 and ∇r2=2x; Euler's identity x⋅∇q=kq holds for homogeneous q of degree k; hence for homogeneous p of degree l and q of degree l−1: Δ(xip)=2∂ip and Δ(r2q)=(4l+2)q+r2Δq (The Laplacian of a C2 function and of a C2 vector field, Directional derivatives and partial derivatives of a map U⊆Rm→Rn, Sums, scalar multiples, products and quotients: (f+g)′(c)=f′(c)+g′(c), (αf)′(c)=αf′(c), (fg)′(c)=f′(c)g(c)+f(c)g′(c), and (f/g)′(c)=(f′(c)g(c)−f(c)g′(c))/g(c)2 when g(c)≠0, Ck Euclidean maps are closed under componentwise algebra and composition, A total derivative computes every directional derivative, and its matrix is the Jacobian, homogeneous polynomial and homogeneous ideal).

[F3]

Ylm(θ,φ)=blmwl∣m∣(cos⁡θ)eimφ/2π for m≥0 and Yl,−m=(−1)mYlm‾; in particular ∂φYlm=im Ylm in the angular chart, and Ylm is continuous (Associated Legendre function normalization (a),(c), The complex exponential by its power series, Sine and cosine defined by their real power series).

[F5]

Lz is self-adjoint on L2(S2,σ) with LzYlm=ℏmYlm, and for F∈H the chart values of LzF are −iℏ∂φF; eigenvectors of Lz for distinct eigenvalues are orthogonal, because ⟨LzF,G⟩=⟨F,LzG⟩ for F,G in the domain of the self-adjoint Lz (Sphere Laplacian diagonal domain (a),(c), Self-adjoint and normal endomorphisms of a finite-dimensional real or complex inner product space, Orthogonality and the orthogonal complement).

[F6]

L3=Lz (equal self-adjoint operators) by Orbital self-adjoint generators (c).

Proof

1.1F2algebra

[(a), the two harmonic pieces] By [F2] and ΔH=0, Δ(QqH)=∑icq,iΔ(xiH)=∑icq,i 2∂iH. Since ∂i commutes with Δ and ΔH=0, each ∂iH lies in Hl−1pol, so Gq=∑icq,i∂iH/(2l+1)∈Hl−1pol; by [F2] and Euler's identity for the homogeneous polynomial Gq of degree l−1, Δ(r2Gq)=6Gq+4(l−1)Gq+r2ΔGq=(4l+2)Gq+r2ΔGq, and here ΔGq=0, so Δ(r2Gq)=(4l+2)Gq=2∑icq,i∂iH. Hence ΔRq=Δ(QqH)−Δ(r2Gq)=0: Rq∈Hl+1pol, and Rq is homogeneous of degree l+1 as the difference of two such polynomials; for l=0 the derivative terms vanish because H is constant, so Gq=0 and Rq=QqH.

2.1step 1.1F1algebra

[(b), degree selection] Restricting the identity of step 1.1 to S2, where r2=1, gives Qq∣S2⋅Ylm=resl+1(Rq)+resl−1(Gq), where for l=0 the second term is omitted because Gq=0; for l≥1 both restriction maps are the defined maps in [F1]. This is an element of Vl+1+Vl−1, using H∣S2=Ylm ([F1]) and QqH∣S2=(Qq∣S2)Ylm; the sum is direct and each summand lies in the corresponding block, so orthogonality Vl+1⊥Vl′ and Vl−1⊥Vl′ for l′∉{l−1,l+1} ([F1]) gives ⟨Qq∣S2Ylm,Yl′m′⟩=0 for such l′.

3.1step 2.1F3F4F5algebra

[(c), weight selection] Let F:=Qq∣S2⋅Ylm∈H by step 2.1. On the chart, by [F3] and [F4], ∂φF=(∂φQq)Ylm+Qq ∂φYlm=iq F+im F=i(m+q)F; hence by [F5] LzF=−iℏ∂φF=ℏ(m+q)F in H. If now m′≠m+q, then using the self-adjointness of Lz ([F5]) and LzYl′m′=ℏm′Yl′m′, ℏ(m+q)⟨F,Yl′m′⟩=⟨LzF,Yl′m′⟩=⟨F,LzYl′m′⟩=ℏm′⟨F,Yl′m′⟩, so ⟨F,Yl′m′⟩=0.

4.1step 2.1step 3.1F6∎

[(d), the rules] Clause (d) restates steps 2.1 and 3.1 for the multiplier Qq: a nonzero angular integral requires l′∈{l−1,l+1} and m′=m+q; the case l′=l−1 presupposes l≥1 because −l′≤m′≤l′ with l−1≥0; and by [F6] the weight m is the L3-eigenvalue in units ℏ, so the multiplier Qq shifts the L3-eigenvalue by ℏq.

Depends on

Dependency tree · 2 levels

Sources