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FSCA184
Prof. Jorge Videla
5 de noviembre de 2017
Pregunta 1, Ejercicio 7.9
Deduce the Lande interval rule, which states that for a given
l and s, the energy difference between two levels differing in j by
unity is proportional to j. Hint: Evaluate Eso in eqn 7.28 for j and
j 1; use the second line in the equation (in terms of nl ).
A partir del capitulo 7 (Atkins y Friedman, 2005), tomamos la segunda
linea de la ecuacion 7.28.
1
Eso (j) Eso (j 1) = hcnl {j(j + 1) l(l + 1) s(s + 1) (j 1)(j) + l(l + 1) + s(s + 1)}
2
(1)
1
= hcnl {j 2 + j j2 + j} (2)
2
1
= hcnl (2j) (3)
2
Eso (j) Eso (j 1) = jhcnl (4)
1
Enlml ; therefore calculate the matrix elements of V = e2 /4o r
and V 2 .
Siguiendo los pasos del hint, tenemos que:
1
2 2
= nlm l |E nlm 2E nlm V + V |nml l (6)
2c2 l l
1 2
2
= Enlm + nlm l |V |nml l 2 nlm l |V |nml l Enlm
(7)
2c2 l l
1 2
nlml |H (1) |nmll = Enlml + nlml |V 2 |nmll 4Enlm2
2
(8)
2c l
1 2
nlml |r2 |nmll =
(10)
a2o (2l + 1)n3
1 1
= 2 (11)
ao (l + 12 )n3
2 (hcRH )2
Luego reemplazando Enlml
= n4
y el operador V sobre el estado
nlml .
2
e2
1 2
4o ao 3(hcRH )2
nlml |H (1) |nmll
= (12)
2c2 (l + 12 )n3 n4
2
e2 40 ~2 40 ~2
Re-definimos (12) en terminos de = 4o ~c , a0 = me e2
= e2
y
e4 c2
RH = 8o h3 c
= 4h
1 ~2 c2 2 32 c4 4
nlml |H (1) |nmll =
(13)
2c2 a2o (l + 21 )n3 4 n4
1 ~2 2 e4 c2 2 32 c4 4
nlml |H (1) |nmll =
(14)
2c2 42 2 2o ~4 (l + 21 )n3 4 n4
1 2 2 2 c2 2 32 c4 4
nlml |H (1) |nmll =
c (15)
2c2 (l + 12 )n3 4 n4
1 2 c4 4 32 c4 4
nlml |H (1) |nmll =
(16)
2c2 (l + 12 )n3 4n4
1 4 2 1 3
nlml |H (1) |nmll =
c (17)
l + 12 n3 4n4
2
5
= 4 c2
8
Luego reemplazando los terminos, = 7, 29735 103 , = me mn
me +mN =
9, 104423456 1031 kg,c = 3 108 m
s
3
orbitals and the energy is a sum of the corresponding energies.
~2 2 3e2 1 1 1 e2 1 1 1
H= (51 + 522 + 523 ) + + + + +
2m 4o r1 r2 r3 4 r r r13
| e {z } | o 12 {z 23 }
H (0) H (1)
~2 2 3e2
H1 = 51
2me 4o r1
~2 2 3e2
H2 = 52
2me 4o r2
~2 3e2
H3 = 523
2me 4o r3
y donde H (1)
e2 1 1 1
H (1) = + +
4o r12 r23 r13
4
the antisymmetry of the wavefunction upon interchange of the
labels of any two electrons.
Para ello consideramos el determinante de Slater (seccion 7.11, capitulo
7, (Atkins y Friedman, 2005)), el cual se define como,
a (1) b (1) . . . z (1)
1 1 a (2) b (2) . . . z (2)
2
(1, 2, ..., N ) =
.. .. ..
N!
. . ... .
a (N ) b (N ) . . . z (N )
Donde representa ms = + 12 y ms = 12 .
(1, 2, 3) 6 = 1s (1)1s (2)2s (3) 1s (1)2s (2)1s (3)
1s (1)1s (2)2s (3) + 1s (1)2s (2)1s (3)
+2s (1)1s (2)1s (3) 2s (1)1s (2)1s (3)
(2, 1, 3) 6 = 1s (2)1s (1)2s (3) 1s (2)2s (1)1s (3)
1s (2)1s (1)2s (3) + 1s (2)2s (1)1s (3)
+2s (2)1s (1)1s (3) 2s (2)1s (1)1s (3)
(2, 1, 3) = (1, 2, 3)
5
ground-state energy for a function of this form, and the correspon-
ding value of z. Calculate the first and second ionization energies.
Hint. Use the variation theorem. All the integrals are standard;
the electron repulsion term is calculated in Example 7.3. Interpret
Z in terms of a shielding constant. The experimental ionization
energies are 24.58 eV and 54.40 eV.
6
Referencias