8.

04 Quantum Physics

Lecture XXII

Radial equation for spherically symmetric potential

using the ansatz (r) = R(r)Y (, ), and inserting for the angular function an eigenfunction Y (, ) = Ylm (, ) = , |l, m, (22-2) we have, using L2 Ylm (, ) = h 2 l(l + 1)Ylm (, ) after dividing by Ylm for the radial equation, h 2 2 2 h 2 l(l + 1) + + + V (r) Rnl (r) = Enl Rnl (r) . (22-3) 2m r2 r r 2mr2 Here, we have added two subscripts n, l to the radial wavefunction R(r) and the eigenenergy E because the SE for the radial part of the wavefunction depends on the total angular momentum l of the 3D wavefunction (r). Note. The z -component of angular momentum Lz , and the corresponding magnetic quantum number m, do not appear in the radial equation. We can dene an l-dependent eective potential, h 2 l(l + 1) , (22-4) 2mr2 where the additional term is the centrifugal barrier for a particle with angular momentum L2 = h 2 l(l + 1). (22-5) Ve,l = V (r) + The radial equation can be brought into a more familiar-looking form by introducing a new function: u(r) = rR(r) (22-6) u(r) R(r) = r Then, u r u u u 2 R = = (22-7) 2 r r r 2 2u 2u R = 2 3 (22-8) r r r u r u u r2 u2r u 2u 2u 2 + 3 R = = (22-9) 2 4 r r r r r 2 2 2 u + R ( r ) = R + R = (22-10) r2 r r r r Massachusetts Institute of Technology XXII-1

8.04 Quantum Physics and the radial equation is 2 h 2 1 2u h l(l + 1) u(r) u(r) + + V (r) =E 2 2 2mr r r 2m r r or h 2 2 h 2 l(l + 1) unl (r) + + V (r) = Enl unl (r) 2 2 2mr r 2m r

Lecture XXII

(22-11)

(22-12)

This equation for u(r) = rR(r) has the same form as the 1D SE in the eective potential h 2 l(l + 1) Ve,l (r) = V (r) + , (22-13) 2mr2 but with slightly dierent boundary conditions. Therefore, u(r) looks like an anti-

Figure I: u(r) = rR(r) has the same form as the 1D SE in the eective potential Ve,l (r), but with slightly dierent boundary conditions. symmetric solution in all space. Consequences are, e.g., that since an antisymmetric

Figure II: u(r) looks like an antisymmetric solution in all space. bound state does not always exist in 1D, that a bound state does not always exist in 3D (in contrast to 1D, where a symmetric bound state always exist in a potential well). 3D wavefunctions u(r) are like antisymmetric 1D wavefunctions in the eective potential h 2 l(l + 1) Vl (r) = V (r) + . (22-14) 2mr2 Massachusetts Institute of Technology XXII-2

8.04 Quantum Physics

Lecture XXII

Hydrogen atom
Ze2 (and the radial equation is) V (r) = 4r h 62 2 Ze2 h 2 l(l + 1) + E u(r) = 0 2m r2 4r 2mr2 (22-15) (22-16)

|E | 2 We introduce a dimensionless position coordinate by 2 = 8m r , and dene for h2 E<0 2 2 2 Ze 8m h Ze 8m h 2 = (22-17) r16|E | h 16hr |E | 8m|E | 2 8m m 1 Ze2 = (22-18) 4h 2|E | =: (22-19)

The equation can be written as 2 u+ 2 with =

Ze2 4h

m 2|E |

1 l(l + 1) u=0 4 2 mc2 e2 = Z 2 , where = 4 |E | hc

(22-20)
1 137.0...

is the dimen-

sionless ne structure constant. To solve this equation, we proceed as for the HO: We write a Taylor-expansion solution after having factored out the correct asymptotic behavior. For very large we have d2 1 u= u 2 dp 4 u() e 2 For very small , d2 l(l + 1) u= u 2 dp 2 u() l+1 Consequently, we try a solution of the form u() = s()l+1 e 2 Massachusetts Institute of Technology
1 1

(22-21) (22-22)

(22-23) (22-24)

(22-25) XXII-3

8.04 Quantum Physics

Lecture XXII

1 1 u () = s ()l+1 + s()(l + 1)l sl+1 e 2 (22-26) 2 u () = s l+1 + 2(l + 1)s l + s(l + 1)ll1 (22-27) 1 s l+1 + (l + 1)sl (22-28) 2 1 1 1 s l+1 + (l + 1)sl sl+1 e 2 (22-29) 2 2 s (l + 1)l l+1 1 l+1 = e 2 s + 2(l + 1) + ss s+ s 2 4 (22-30) 1 l(l + 1) 1 l(l + 1) u = l+1 e 2 s (22-31) 2 4 4 2 Inserting this into (??) leads to 2(l + 1) (l + 1)l l + 1 1 1 l(l + 1) s + 1 s + + + s = 0 (22-32) 2 4 4 2 2l + 2 l1 s + 1 s + s=0 (22-33) To solve this dierential equation, we write a Taylor expansion about = 0: s() = s = =
k=0 k=0

a k k ak k (k 1)k2 ak+2 (k + 2)(k + 1)k

(22-34) (22-35) (22-36) (22-37) (22-38) (22-39)

k=0 2l + 2 2l + 2 1 s = 1 ak kk1 = (2l + 2) ak+2 (k + 2)k ak+1 (k + 1)k k=0 l1 s = ( l 1) ak+1 k k=0

which substituted into (??) results in

k (k + 2)(k + 1)ak+2 + 2(l + 1)(k + 2)ak+2 + ( l 1 k 1)ak+1

= 0 (22-40) XXII-4

Massachusetts Institute of Technology

8.04 Quantum Physics This must vanish term by term, so we obtain a recursion relation (k + 2)(k + 2l + 3)ak+2 = (k + l + 2 )ak+1 or ak+1 k+l+1 = ak k + 1 k + 2(l + 1) recursion relation for expansion coecients

Lecture XXII

(22-41)

(22-42)

1 If the series does not break o somewhere, we will have for large k , ak k ak1 or 1 + ak k! , which gives a growth s() e , which is not acceptable for u() = s()e 2 . Consequently, we require the series to terminate, which implies = k + l + 1 for some L. Let us call nr = k the integer with that property. It is cutomary to dene the principal quantum number as

n = nr + l + 1 , where nr 0, so n 0, so n l + 1, n integer, and Ze2 m n = 4h 2|En | mc2 = Z 2|En | =n Consequently, the eigenenergies of the hydrogen atom are 1 (Z)2 En = mc2 2 n2 eigenenergies of hydrogenlike atoms

(22-43)

(22-44) (22-45) (22-46)

(22-47)

This is the same energy eigenspectrum as obtained from the Bohr formula. Note. There are important dierences: The principal quantum number n = nr + l + 1 is really the sum of the radial quantum number nr and the total angular momentum quantum number l. We have obtained the full radial and angular distribution of the electron, which generalizes the classical concept of an orbit. Massachusetts Institute of Technology XXII-5

8.04 Quantum Physics

Lecture XXII

First few radial functions

2 n =

8m|En | 2 r h 2 8m 1 (Z)2 2 = 2 mc2 r n2 h 2 (2mcZ)2 2 = r hn 2 2 2Z 1 = r2 2 a0 n 2Zr = na0

(22-48) (22-49) (22-50) (22-51) (22-52)

with the Bohr radius a0 = Consequently, e 2 = e

h 2 mc

(22-53)

1. nr = l = 0, n = m = , a1 = 0 u(r) = Ce R(r) =
1 2

= C1

Zr Z e a0 a0

(22-54) (22-55)

u(r) Zr = C2 e a0 r

Note. The probability to nd the electron between r and r + dr is given by r2 |R(r)|2 dr = |u(r)|2 dr. 2. (a) nr = 1, l = 0, n = 2 = 1 1 a1 = = 12 2 a0 1 Zr 2Zr Zr u20 (r) = Ce (1 ) = C 1 e a0 2 a0 2a0 Zr 2Zr R20 (r) = C 1 e a0 2a0
1 2

(22-56) (22-57) (22-58) XXII-6

Massachusetts Institute of Technology

8.04 Quantum Physics (b) nr = 0, l = 1, n = 2 = a1 = 0 2 Zr 2 1 Zr 2 u21 (r) = C e =C e 2a0 a0 Zr 2Zr e a0 R21 (r) = C a0 a1 =0 a0

Lecture XXII

(22-59) (22-60) (22-61)

R20 = Rn=2,l=0 and R21 = Rn=2,l=1 are dierent states that have the same eigenenergy. The occurrence of dierent eigenstates with the same energy, (or in general quantum number) is called degeneracy.

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XXII-7