Group Problems #34 - Solutions

Monday, November 21

Problem 1

The radial wavefunction

An electron in a hydrogen atom is in a 3d state. (a) What are the principle quantum number and angular momentum quantum number for this electron? For a 3d state, we have n = 3 and = 2.

(b) What is the radial wavefunction for this electron? (Hint: L5 0 = 1) From the notes, we have: R(r) = 2 na0
3/2

(n 1)! r/na0 e 2n[(n + )!]

2r na0

+1 L2 n 1

2r na0

(1)

where the last parentheses denote the argument of the associated Laguerre poly+1 nomials, L2 = 2, so the polynomial n 1 . For the 3d state, we have n = 3 and = 1. Evaluating the other constants gives: term is L5 0 R3,2 (r) = 2 3a0
3/2

1 r/3a0 e 6(5!)

2r 3a0

L5 0

(2) (3) (4) (5) (6) (7) (8)

1 2 r/3a0 2 2 4 r e = 2 3 / 2 (3a0 ) 9a0 12 5 1 2 2 2 r2 er/3a0 = 3 / 2 (3a0 ) 27 5 a0 = (A3,2 ) r e where A3,2 is a constant.

2 r/3a0

2 (c) What is the most probable radius to nd the electron? The most probable radius for the electron can be found by taking the derivative of the probability density, r2 R2 (r) with respect to r and setting this to zero. In particular,
2 2 6 2r/3a0 r2 R3 ,2 (r ) = (A3,2 ) r e

(9) (10) e2r/3a0 (11) (12)

2 d(r2 R2 ) = (A3,2 )2 6r5 e2r/3a0 + r6 dr 3a0 = (A3,2 )2 r5 e2r/3a0 6 2r = 0. 3a0

(13)

Eqn. (13) is true at r = 0, r = , and when the expression in square brackets is zero. The rst two options are not interesting, thus we have: 6= 2r = r = 9a0 . 3a0 (14)

Problem 2

High angular momentum orbitals in hydrogen

Show that for those orbitals with the largest possible angular momentum, the most probable radius for the electron is quantized. We follow a similar procedure as problem 1(c), starting with the general expression in Eqn. (1). The states with maximum possible angular momentum have = n 1, so the radial wavefunctions become:
2 2n 2r/na0 Rn (r) = An er/na0 rn1 = r2 Rn (r) = A2 e , nr

(15)

where the constant An has all the terms not containing r. As above, now we just need to take the derivative of r2 R2 and set it to zero: 2 d(r2 R2 ) 2n1 2r/na0 = A2 e + r2n n 2n r dr na0
2n1 2r/na0 = A2 e n n 2r

e2r/na0

(16) (17)

r =0 na0

(18) (19)

= r = n2 a0 .

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