/12

Universidad Complutense de Madrid

Departamento de Fsica Te
orica I

. 11

Mec
anica cu
antica avanzada - Problemas resueltos
(Licenciatura en Fsica, 4 o curso)

van

PROBLEMA. Un
atomo de hidrogeno se ve sometido a una perturbacion
(
0
t<0
,
V =
f (r) a P
t0

.A

donde r = |x| es la distancia radial, f (r) es una funcion que depende s

olamente de r y a es un
vector constante conocido.
(i) Calcular las reglas de selecci
on para el momento angular en la aproximacion de Born para la

transicion |n, , mi |n , , m i.

f (r) =

uan

(ii) Es posible a este orden en teora de perturbaciones una transicion entre estados con el
mismo n
umero cu
antico n? Razonar la respuesta. En caso de serlo, calcular la probabilidad
de transicion en un tiempo T para n = n = 2 y = 0 y una funcion
f0
r

r > 0,

c. C

con f0 una constante de dimensiones adecuadas.

(expresiones finales en rojo).
SOLUCION

The transition probability in Borns approximation is given by

 Z T
1
(0, T ) = 
dt ef i t Vf i
~ 0

Me

P := P

(B)
if

where

|ii = | ni i mi i ,

|f i = | nf f mf i ,

Ef Ei  1
1  m (Zc)2

=
,
~
2~
n2i
n2f

M-

f i =

UC

Vf i = hf | f (r) aP |ii =

F. Ruiz

2

 ,


3
X
j=1

aj hf | f (r) P j |ii .

UCM - Mecanica cuantica avanzada

. 11

if ni = nf
if ni 6= nf

 2
P = Ff i (T ) Vf i  .

van

it follows that

/12

Taking into account that Vf i does not depend on t and noting

T2

2
Z T



T

Ff i (T ) := 
dt eif i t  =
sin2 f2i

f i T
2

(i) The selection rules are those for Vf i . Being f (r) a scalar and P a vector, the perturbation
operator V has = 1. The selection rules for the angular momentum are then
f i = 1, 0, 1

and f = 1 if f = 0.

f i = 1, 1

.A

Since P is odd, the state |n, , mi must change its parity. Hence

and f = 1 if f = 0.

i~ j
P we write Vf i as
m
Vf i

3


m X j
a hf | f (r) xj H0 H0 xj |ii .
=
i~
j=1

c. C

Using [X j , H0 ] =

uan

(ii) The Hamiltonian for the Hydrogen atom is


 2
Ze2
~2
2
L2

Ze2
P2
+
=
+
+
.
+
H0 =
2m
|x|
2m r 2
r r
r2
r

(1)

The first term in this expression is straightforward,

j=1

aj hf | f (r) xj H0 |ii = Ei hf | f (r) ax |ii .

(2)

Me

3
X

As regards the second one, note that H0 cannot be pulled to the left to act on hf | since f (r) is on
the way. To reach hf |, H0 must first commute with f (r),
f (r) H0 = [f (r) , H0 ] + H0 f (r) .
This and

imply that

j=1

F. Ruiz

 E

~2 D   2


a hf | f (r) H0 x |ii =
f  f + f + 2f
ax  i + Ef hf | f (r) ax |ii .
2m
r
r
j

UC

3
X

M-




2
~2

f (r) + f (r) + 2 f (r)

[H0 , f (r)] =
2m
r
r

(3)

UCM - Mecanica cuantica avanzada

/12

Substituting (2) and (3) in (1), recalling that the bound states |nmi = |ni |mi for the Hydrogen
atom have wave functions (r, , ) = Rn (r) Y m
(, ), employing

. 11

ax
r

ax = r

and noting that ax/r does not depend on r, we obtain

Vf i = i Rf i Af i ,

van

where Rf i and Af i stand for the radial and angular contributions,


E
m
d  
~ D

n

(Ef Ei ) hnf f | f (r) |ni i i +

nf f  rf + 4f + 2rf
 i i ,
~
2
dr
 ax 
E
D


= f mf 
 i mi .
r

Af i

.A

Rf i =

Let us look at the radial contribution Rf i for nf = ni . In this case the difference Ef Ei
vanishes and the first term in Rf i is zero, so that

d   E
~ D

n f  rf + 4f + 2rf
n i ,
2
dr

uan

Rf i =

n = nf = ni .

This is in general different from zero, hence transitions i f with nf = ni are allowed. Take
ni = nf = 2, i = 0 and f (r) = f0 /r. In this case the only possible value for f is 1 and

We recall that
R20 (r) =

1
3/2
2 a0

c. C

D  1
1 d   E

Rf i = ~ f0 2 1 2 +
2 0 .
r
r dr

r  r/2a0
e
,
1
2a0

1
r r/2a0
e
,
R21 (r) = 3/2
2 6 a0 a0

Me

where a0 is Bohrs radius. Some integration then gives

~f0
.
12 a20

Rf i =

where we have used that

M-

The angular part Af i reproduces the selection rules already found. To compute it, we choose
the Oz axis in the integral parallel to the direction defined by the vector a, so that
r
Z



m 
4
mf
mi
i
.
Af i = a d Y f (, ) cos Y i (, ) =
a Y f f  Y 01 Y m

i
3
|
{z
}

F. Ruiz

UC

cos =

Clebsch-Gordan coeff

r
3

4 0
Y1
3

UCM - Mecanica cuantica avanzada

/12


The matrix element in blue is the Clebsch-Gordan coefficient hf mf  1 0 ; i mi i. For ni = nf = 2,
i = 0, which in turn implies f = 1, mi = mf = 0. It is clear that

. 11

a
Af i = .
3

Putting everything together, the probability becomes

~2 f02 |a|2 2
T .
24 33 a40

van

P (2s 2p) =
This is only valid for T such that P 1.

Comment. The expression of Rf i can be further elaborated. To this end recall that

.A

Rn (r) = Cn e/2 L2+1

n1 () ,

Using that

uan

where Lk () are the generalized Laguerre polynomials and the constant Cn and the dimensionless
variable are given by


2
2r
(n 1)! 1/2
Cn =
.
, =
3/2
2
(n
+
)!
a
0n
n a0
d q
Lp (x) = (p + 1) Lqp+1 (x) (p + q + 1 x) Lqp (x) ,
dx

x
we have

All in all,


p
(n + 1)2
r
n 1 Rn (r) + (n ) (n + + 1)
Rn+1, (r) .
na0
n2

c. C

d
Rn (r) =
r
dr

m
(Ef Ei ) hnf f | f (r) |ni i i
~
h

E
r  i 
~ D

nf f  rf + 2 1 ni +
f ni i
+
2
n i a0
p
 

(ni + 1)2

nf f  f ni + 1, i
+ ~ (ni i ) (ni + i + 1)
2
ni

Me

Rf i =

M-

For f (r) = r s , with s an integer, all the integrals in this expression are of the form (see Appendix A
in [Galindo & Pascual])
Z

dx ex x Lqp (x) Lqp (x)
I (pq; p q ) :=
0
min(p,p )

= !

()p+p +k

F. Ruiz

UC

k=0

q
pk

 

q
p k

 


1
,
k

UCM - Mecanica cuantica avanzada

q
p

= ()


q+p1
,
p

. 11

for q p 0
 
q
= 0 for
p

p > q > 0.

F. Ruiz

UC

M-

Me

c. C

uan

.A

van

and

/12

where the binomial coefficients are given by

 
q!
q
=
p
p! (q p)!

UCM - Mecanica cuantica avanzada

/12

. 11

PROBLEMA. El hamiltoniano de un sistema formado por dos partculas de masas m1 y m2 tiene

la forma
P2
P2
H = 1 + 2 + V (|x1 x2 |) .
2m1 2m2

van

Los autoestados y autofunciones de H son conocidos. Durante un tiempo la partcula 2 experimenta una colisi
on que le comunica una velocidad v. Supongase que << 1 y que |v| << a0 ,
no cl
asico del sistema. Si inicialmente el sistema se encuentra en su estado
donde a0 es el tama
fundamental, cacular la probabilidad de que como consecuencia de la colisi
on el sistema salte al
primer estado excitado.
Particularizar para el caso de un sistema unidimensional con una interacci
on vibratoria entre
las partculas de frecuencia angular 0 .

.A

(expresiones finales en rojo).

SOLUCION

Before the kick, the system is a standard two-body problem. The positions and momenta of
the center of mass (com) and the reduced (red) particle are
m1 x1 + m2 x2
,
m1 + m2

P = p1 + p 2 ,

uan

R=

r = x1 x2 ,

p=

m2 p1 m1 p2
,
m1 + m2

with the total mass M and the reduced mass being given by
=

m1 m2
.
m1 + m2

c. C

M = m1 + m2 ,

The hamiltonian H of the system can be writen as (the hats here denote operators)
H=

Me

It can be splitted

2
2
P
p
+
+ V (|r|) .
2M
2

H = Hcom + Hred ,

in a center of mass part Hcom and a reduced part Hred ,

~2
R
2M

Hred =

M-

Hcom =

~2
r + V (r) .
2

The total wave function is

(R, r, t) = ei ( Ecom tPR)/~ (r, t) ,

with

F. Ruiz

UC

Ecom =

P2
2M
UCM - Mecanica cuantica avanzada

/12

the com energy and and (r, t) the solution to the reduced Schr
odinger equation

(r, t) = Hred (r, t) .

t

. 11

i~
The reduced stationary states are

(r, t) = eiEredt/~ t/~ (r) ,

Hred (r) = Ered (r) .

van

After the kick, particle 2 has position x2 = x2 + vt and momentum p2 = p2 + m2 v. The

total hamiltonian becomes
2
2
P
1
P
1
+ 2 + m2 v2 + P2 v + V (|x1 x2 vt|)
H =
2m1 2m2 2
2
2
1
m2
p
P
v +
+ m2 v 2 +
+ V (|r vt|) .
Pv p
=
2M
2
M
2

.A

Its splitting

H = H com + H red

uan

in com and red parts is now given by

2
P
1
m2
+ m2 v 2 +
Pv
2M
2
M
2
p
+ V (|r vt|) .
=
p v +
2

H red
The total wave function now reads

c. C

H com =

(R, r, t) = ei (E com tPR)/~ (r, t)

where the com energy E com is

1
m2
P2
+ m2 v 2 +
Pv
2M
2
M

Me

E com =

(4)

and the reduced Schr

odinger equation takes the form
i~

(r, t) = H red (r, t) .
t

M-

v from H red , we make

To remove the term p
(r, t) = eivr/~ (r, t) .

This gives

F. Ruiz

h ~2
i

(r, t) =
r + V (|r vt|) (r, t) .
t
2

UC

i~

(5)

(6)

UCM - Mecanica cuantica avanzada

/12

. 11

We remark that in eqs. (4)-(5) with the solution to the Schr

odinger equation (6) is the exact
wave function after the kick. Note that there is no reason for the dependence of (r, t) on t to be
through r vt. The approximations come next.
The sudden approximation establishes that the probability that the system jumps from a state
i before the kick to a state f after the kick is given by
2

2





P =  h f (R, r, ) | i (R, r, ) i  =  h eivr/~ f (r, ) | i (r) i  .

van

odinger equation (6) after

The states f , that is, the solutions to the reduced time-dependent Schr
the kick do not follow from this approximation. We must find them by other means.
The region where the potential V (r) is dominant is1 |r| a0 . This and the assumption |v| a0
implies the approximation
f (r, t) eiEred t/~ f (r) for

a0
,
|v|

.A


with f (r), Ef,red solutions for the unperturbed time-independent reduced hamiltonian Hred .
The pobability for the transition i (R, r, 0) f (R, r, ) is then

uan


2
 ivr/~

P = he
f (r) | i (r) i  .

If the particles move in one dimension and interact through a harmonic oscillator potential, the
reduced hamiltonian takes the form
1
~2 d2
+ 2 x2 .
2
2 dx
2

c. C

Hred =

The wave functions i are

r

2 2
n (x) = n
Hn (x) e x /2 ,
2 n!

n = 0, 1, . . . ,

,
~

Me

where Hn (z) are the Hermite polynomials. If the oscillator is initially in its ground state, the
probability for it to be in its first excited state after the kick is
2

v 2 v2 /2~


P (v) =  h eivx/~ 1 (x) | 0 (x) i  =
.
e
2~

M-

The approximation is valid if P 1. Since the exponential is bounded from above by 1, this
requires 12 v 2 ~, that is, the kinetic energy gained by particle 2 is much smaller than the
energy of the ground state. In the regime 21 v 2 ~ the probability also becomes very small.
Equating to zero the first derivative of P (v) with respect to v, we have
P (v0 ) = 0

1 2
v = ~ .
2 0

F. Ruiz

UC

Recall, for example, that the probability density for the ground state of the hydrogen atom has its maximum at
|r| = aBohr .

UCM - Mecanica cuantica avanzada

/12

This corresponds to a maximum, since

. 11

P (v0 ) < 0 .
The probability is then bounded from above by

F. Ruiz

UC

M-

Me

c. C

uan

.A

van

P (v) P (v0 ) = e1 0.368 .

UCM - Mecanica cuantica avanzada

/12

. 11

PROBLEMA. Un
atomo de hidrogeno experimenta una transicion 3p 2p emitiendo un foton.
Indicar de que tipo de transicion se trata.
(expresiones finales en rojo).
SOLUCION

Let be the angular momentum of the operator O that mediates the transition
ni = 3, i = 1, mi

nf = 2, f = 1, mf .

van

Composition of angular momenta,

i = i + , . . . , |i | f ,
implies that
1 1 = 2, 1, 0

.A

1 2 = 3, 2, 1

1 = + 1, . . . , 2 for 3 .

uan

The only allowed values for are then = 1, 2. Since the initial and final states have the same
parity, i = f = 1, the operator O must have O = +1. The case = 1 corresponds to dipole
magnetic transitions, and = 2 to quadrupole electric transitions. The dipole magnetic transition
amplitude is proportional to
(k ) hnf f mf |L|ni i mi i = (k ) hnf f |ni i i hf mf |L|i mi i .

3
X

i,j=1

c. C

In the case at hand, i = f . Recalling that hnf i |ni i i = ni nf , we conclude that the transition
cannot be of this type. The amplitude for a quadrupole electric transition is proportional to
ki j hnf f mf |xi xj |ni i mi i = hnf f |r 2 |ni i i

3
X

i,j=1

ki j hf mf |

xi xj
|i mi i .
r2

Me

The angular integrals are different from zero. As for tha radial part we have
h21|r 2 |31i =
Hence,

213 35 2
aB 6= 0 .
57

M-

= 2 : Quadrupole electric transition.

F. Ruiz

UC

Comment. Higher multipole transitions are forbidden. Quadrupole magnetic transitions (M2)
change parity, and octupole electric (E3) and magnetic (M3) do not allow i = 1 f = 1.

10

UCM - Mecanica cuantica avanzada

/12

. 11

PROBLEMA. Sobre un oscilador arm

onico unidimensional de frecuencia angular , que en
ti se encuentra en el estado fundamental, actua un campo externo cuya contribucion al
hamiltoniano es


V (x, t) = V0 (x + vt) (x vt) .
Calcular la probabilidad de que salte al primer estado excitado (tf ).

(expresiones finales en rojo).

SOLUCION
 (B) 2
(B)
P if = Aif  ,
(B)
Aif

1
=
~

dt ei f i t Vf i .

.A

(B)

where Aif is given by

van

The transition probability in Borns approximation is

vt

uan

We first compute Vf i . At a given t, as a funtion of x, the perturbation V (x, t) is rectangular pulse

that extends from vt to vt. Hence
Z vt
Vf i = V0
dx f (x) i (x)
The eigenfunctions and eigenvalues of the one-dimensional harmonic oscillator are
r
r


1
2 x2 /2

n (x) =
, =
, n = 0, 1, . . .
Hn (x) e
, En = ~ n +
2
~
2n n!

c. C

They have definite parity

n (x) = ()n n (x) .

If |ii = |0i and |f i = |1i, the matrix element Vf i = V10 is the integral over a symmetric interval of
an odd funtion, hence it vanishes,
V10 = 0 .

Me

It follows that

(B)

P 0 1 = 0 .
(n)

We move on to higher orders in perturbation theory. To nth order the amplitude Aif involves a
chain of matrix elements
X
hf |V |kn1 i hkn1 |V |kn2 i hk1 |V |ii .
(7)

M-

k1 ,...,kn1

F. Ruiz

UC

Since the perturbation V is even in x, the parity of |ii must be the same as that of |k1 i, and this
the same as that of |k2 i, and so on. The final state |f i must then have the same parity as |ii;
otherwise the product (7) vanishes. We conclude that the transition amplitude for |0i |1i is zero
to all orders in perturbation theory,
(n)
P 0 1 = 0 .
11

UCM - Mecanica cuantica avanzada

vt

/12

2 2
dx 2 2 x2 1 e x .

vt

Integrating by parts the first term in the integrand, we obtain

r
2 2 2
2
V20 =
V0 vt e v t .

It then follows that

=

2 V0 v
~

2 v2 t2

dt t e

and from this

(B)

P 02 = 2

V0
v 2

2

(B)

2it

i 2 V0 2 /2 v2
,
e
=
~ 2 v 2

.A

(B)
A02

van

V20

V0
=
2

. 11

Comment 1. Assume |ii = |0i and |f i = |2i. In this case,

e2~/v .

uan

Borns approximation is valid if P 02 1. This occurs for:

(B)

(i) ~ v 2 . The exponential decreases very quickly and P 02 becomes very small. The
quantity v 2 /2 can be thought of as a kinetic energy communicated by the pulse to the
oscillating particle. It must be much smaller than the ground state energy ~/2. This regime
is independent of V0 .

c. C

(ii) V0 v 2 . That is, the height of the pulse is much smaller than the kinetic energy it
(B)
communicates to the oscillator. Under this assumption, it is trivial that P 02 1. This
regime is independent of the relation between v 2 and ~.
(B)

Me

Comment 2. An alternative approach is to integrate in Aif first over t and then over x. The
easiest way to perform the integral over t is to use that the Fourier transform of the Heaviside
function (s) is given by
Z
1
ds ei s (s) = i PP + () .

M-

This implies, after making the change x vt = s, that



Z
1
i f i t
i f i x/v
+ (f i ) .
dt e
(x vt) = e
i PP
f i

F. Ruiz

UC

Since by assumption f i is different from zero, the Dirac delta does not contribute and the principal
part can be removed. Hence
Z




i
ei f i x/v + e i f i x/v .
dt ei f i t (x + vt) (x vt) =
f i

12

UCM - Mecanica cuantica avanzada

Using for the Fourier transform of the function f (x) at k the notation
Z


dx eikx f (x) ,
F f (x) (k) =

the amplitude in (8) takes the form

(B)

Aif =

/12

(8)

van

. 11

With this, the amplitude in Borns approximation can be written as

Z


iV0
(B)
dx ei f i x/v + e i f i x/v f (x) i (x) .
Aif =
~f i


 f i

iV0
F f (x) i (x)
+ (v v) .
~f i
v

.A

Note that if f (x) i (x) is odd, the integral (8) vanishes, as we already know. For f (x) i (x)
even, both terms in (8) give the same contribution.
Comment 3. Consider now



V (x, t) = V0 2 (x) (x + vt) (x vt) .

F. Ruiz

UC

M-

Me

c. C

uan

It is very easy to show that in this case transitions occur between states with opposite parity.

13

UCM - Mecanica cuantica avanzada