PRUEBA II

FSCA184
Prof. Jorge Videla

Duilio Marcelo Fonseca Gallardo

Licenciatura en Ciencias m/Fsica
Universidad Austral de Chile

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.

2~2 {j(j + 1) l(l + 1) s(s + 1)} < ls ; jmj |(r)|ls ; mj >

1
= hc{j(j + 1) l(l + 1) s(s + 1)}
2 (7.28)
 j(j + 1) l(l + 1) s(s + 1)
= Z 4 2 hcR
2n3 l(l + 21 )(l + 1)

Evaluando la Ec.7.28, en j y j 1, tendremos que.

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)

Donde de (4) podemos concluir que, la diferencia de energa entre dos

nivele que difieren en j unidades, es proporcional a j.

Pregunta 3, ejercicio 7.13

Find the first-order corrections to the energies of the hydro-
gen atom that result from the relativistic mass increase of the
electron. Hint: The energy is related to the momentum by E =
1
(p2 c2 + m2 c4 ) 4 + V . When p2 c2 << m2 c4 , E c2 + p2 /2 + V
p4 /83 c2 , where the reduced mass mu has replaced m. Ignore the
rest energy c2 , which simply fixes the zero. The term p4 /83 c2
is a perturbation; hence calculate < nlml |H (1) |nlml >= (1/2mc2 ) <
nlml |(p2 /2)2 |nlml >= (1/2mc2 ) < nlml |(Enlml V )2 |nlml >. We know

1
Enlml ; therefore calculate the matrix elements of V = e2 /4o r
and V 2 .
Siguiendo los pasos del hint, tenemos que:

nlml |H (1) |nmll = 2

 
nlm l |(E nlm V ) |nml l (5)
2c2 l

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

A partir del teorema de Virial (Seccion 2.7 de (Atkins y Friedman, 2005)),

podemos definir E en terminos de V.
1
< E >= <V >
2
Luego re-definiendo V en terminos de Enlml .

1  2
nlml |H (1) |nmll = Enlml + nlml |V 2 |nmll 4Enlm2


 
2
 (8)
2c l

nlml |H (1) |nmll = nlml |V 2 |nmll 3Enlml 

  
2
(9)
2c

Como V = e2 /4o r depende de r, a partir de la ecuacion 6.183 del

capitulo 6 de (Zettili, 2009) tendremos que,

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

Utilizando los valores del estado de energa basal, n = 1, l = 0, ml = 0.

E (1) = 100|H 1 |100



5
= 4 c2
8
Luego reemplazando los terminos, = 7, 29735 103 , = me mn
me +mN =
9, 104423456 1031 kg,c = 3 108 m
s

E (1) = 1, 452 1022 J

Finalmente calculamos la correccion de primer orden del estado basal de

energa,

E (1) 1, 452 1022 J

=
hc (6, 626 1034 Js)(3 108 m
s)
= 7, 305 102 m1

Pregunta 4, Ejercicio 7.14

Write the hamiltonian for the lithium atom (Z = 3) and con-
firm that when electron?electron repulsions are neglected the wa-
vefunction can be written as a product (1)(2)(3) of hydrogenic

3
orbitals and the energy is a sum of the corresponding energies.

Dado que el Hamiltoniano para un atomo hidrogenoide (capitulo 3 (Atkins

y Friedman, 2005)), esta dador por:

~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)

donde podemos definir

H (0) + H (1) = H, con H (0) = H1 + H2 + H3

~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

Luego aplicando H (0) sobre (1)(2)(3).

H (0) (1)(2)(3) = (H1 + H2 + H3 )(1)(2)(3)

= H1 (1)(2)(3) + (1)H2 (2)(3) + (1)(2)H3 (3)
= (E1 + E2 + E3 )(1)(2)(3)
H(0) (1)(2)(3) = E0 (1)(2)(3)

Pregunta 5, Ejercicio 7.15

Write the explicit expression for the Slater determinant corres-
ponding to the 1s2 2s1 ground state ofatomic lithium. Demonstrate

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 ) 

Para construir el determinante de Slater del litio atomico, debemos de-

finir Z = 3 (lito), y considerar los estados posibles dados por 1s2 2s1 .
 
 (1) (1) (1) 
 1  1  1s 1s 2s 
2  (2) (2) (2) 
(1, 2, 3) =  1s 1s 2s
3!  (3) 

 1s (3) 1s (3) 2s

Donde representa ms = + 12 y ms = 12 .

Desarrollando el determinante, tendremos que

(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)

Finalmente evaluando (2, 1, 3) para demostrar la anti-simetra

(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)

Pregunta 6, Ejercicio 7.17

Take a trial function for the helium atom as , with c(1)(z3/p)1/2ezrl
and c(2) (z3/p)1/2ezr2, z being a parameter, and find the best

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

Atkins, P., y Friedman, R. (2005). Molecular quantum mechanics. Oxford

University Press.
Zettili, N. (2009). Quantum mechanics: Concepts and applications. Wiley.