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CHAPT ER 2
Schrödinger Equation
and Wave Function
1 q2 q q
= − 2
∇2 ψ + A2 ψ − p Aψ − A · pψ + qφψ
2m c2 c c
1 q q q2
= − 2
∇2 ψ + 2i A · ∇ψ + i ψ∇ · A + A2 ψ + qφψ .
∂ψ
The Schrödinger equation i = Hψ becomes
∂t
∂ψ 2 2
q1 q2
i =− ∇12ψ − ∇ 2ψ + ψ,
∂t 2m1 2m2 2 r12
where
∂2 ∂2 ∂2
∇2i = + 2 + 2, i = 1, 2 .
∂x i
2
∂y i ∂z i
2.5 Starting from the Schrödinger equation for ψ, obtain the equation for
ψ∗.
∂ψ ∗ 2
−i =− ∇2 ψ ∗ + V ∗ (X, t)ψ ∗ .
∂t 2m
2.6 If E1 and E2 are the eigenvalues and φ1 and φ2 are the eigenfunctions
of a Hamiltonian operator then find whether the energy corresponding
to the superposition state φ1 + φ2 is equal to E1 + E2 or not.
2
2.7 Express the Schrödinger equation − ∇2 + V (x, y, z) ψ(x, y, z) =
2m
+V (ξ, η, φ) ψ = Eψ .
2.8 Find the condition under which both ψ(X, t) and ψ ∗ (X, −t) will be the
solutions of the same time-dependent Schrödinger equation.
The Schrödinger equations for ψ(X, t) and ψ ∗ (X, −t) are given by
∂ψ 2
i = − ∇ 2 ψ + V (X, t)ψ ,
∂t 2m
∂ψ ∗ 2
2
i =
− ∇ ψ ∗ + V ∗ (X, −t)ψ
∂t 2m
2.9 What is the major difference between real and complex wave functions?
J= [ψ ∗ ∇ψ − ψ∇ψ ∗ ] .
2mi
2.10 What is the difference between the wave function ψ1 = ei(kx−ωt) and
ψ2 = ei(k·X−ωt) ?
2.13 Write the operator forms of kinetic energy and angular momentum L =
r × p.
1 p2 2
(K.E.)op = mv 2= = − ∇2 .
2 2m 2m
i j k
L = r×p = x y z
px py pz
= i (ypz − zpy ) + j (zpx − xpz ) + k (xpy − ypx ) .
∂ ∂ ∂ ∂
Ly = i −z +x =i x −z ,
∂x ∂z ∂z ∂x
∂ ∂ ∂ ∂
Lz = i −x +y =i y −x .
∂y ∂x ∂x ∂y
d
2.14 Consider the one-dimensional Schrödinger equation u(x) = − ln ψ(x).
dx
Obtain the Schrödinger equation under the change of variable
d
u(x) = − ln ψ(x).
dx
That is, ux − u2 − λ + g = 0.
2.15 Find the conditions to be satisfied by the functions f and g such that
under the transformation ψ = f (x)F (g(x)) the Schrödinger equation
ψxx + (E − V )ψ = 0 can be written as
Fgg + Q(g)Fg + R(g)F (g) = 0 . (2.1)
Then show that
2
1 Q2 g g
E − V = (g )2 R − Q − + . (2.2)
−
g
2 4 2g 2g
The conditions on f and g are given by Eqs. (2.6). From Eqs. (2.6) we
obtain
f gQ g
= − (2.7a)
f 2 2g
f
E −V = g 2R − . (2.7b)
f
From (2.7a) we find f /f and substituting it in (2.7b) we obtain
d f f f 2
= − . (2.8)
dx f f f2
That is,
f d f 2
= +f
f dx f f2
d gQ 2
= − g +
gQ
−
g
dx 2 2g 2 2g
2
1 g g 2 Q2 g
= Qg − + + . (2.9)
2 2g 4 2g
2.17 Which of the following wave functions are admissible in quantum me-
chanics? State the reasons.
2
(a) e−x . (b) sechx. (c) −x
√ e 2 . (d) tanhx. (e) sin x, 0 < x <2 2π. (f) sin x,
−∞ < x < ∞. (g) e −x . (h) tan x. (i) secx. (j) xe−x . (k) 1 − x2 ,
−1 < x < 1.
√ 1/2
Thus N = 1/ (σ π ) .
2.19 Find the value of N for which the wave function ψ(x) = N for |x| < a
and 0 for |x| > a is normalized.
The normalization condition gives
a a
1 = ψ ∗ ψ dx = N 2 dx = N 2 x|a−a
−a −a
2
= 2aN .
√
Thus, N = 1/ 2a .
2.20 Normalize the wave function ψ = e−|x| sin αx. It is given that
∞
e sin αx dx = α /(1 + α ).
−x 2 2
0
∞
= 2N 2 e−2x sin2 αx dx
0
∞
N 2 −2x ∞ N2
= − e |0 − e−x cos αx dx
2 2 0
∞
N2 N2
= − −e−x cos αx0 |∞ − α e−x sin αx dx
2 2 0
N2 N2 α3
= − 1−
2 2 1 + α2
N 2 α3
= .
2(1 + α2 )
L3 L5 L7
= N2 − +
12 160 448
Thus,
−1/2
L3 L5 L7
N = − + .
12 160 448
= c2 x2 e2x/b dx + c2 x2 e−2x/b dx
−∞ 0
∞
= 2c2 x2 e−2x/b dx .
0
e−b 2
P =1− b + 2b + 2 .
4
J= [ψ ∗ ∇ψ − ψ∇ψ ∗ ] .
2mi
J = [ψ∇ψ − ψ∇ψ] = 0 .
2mi
J = Im(ψ ∗ ∇ψ)
m
= Im A∗ e−i(px x−Et)/ + B ∗ ei(px x+Et)/
m
ipx
+ Be
−i(px x+Et)/
× Aei(px x−Et)/
px 2 2
= |A| − |B| .
m
2
2.25 If the wave function of a particle at t = 0 is ψ(x, 0) = N e−ikx−(x /2a 2)
a π
−x /a
= √ e
m a π
k
= P (x) .
m
dψ dψ ∗
ψ∗ −ψ
=0.
dx dx
Then J = 0. Therefore, for the real Gaussian function J = 0.
2 2
2.27 Verify whether the wave function ψ = N eikx−x /(2a ) satisfies the conti-
nuity equation or not.
∂ρ dJ
The continuity equation is given by + = 0. For the given function
∂t dx
∂ρ
ρ = ψ ∗ ψ = N 2 e−x /a and
2 2
= 0. Further
∂t
dψ
J = Im ψ dx
∗
m 2 2
= Im N 2 e−x /a
ik − x/a2
m
N 2 k −x2 /a2
= e .
m
Then
dJ N2 k 2 2
= −2 xe−x /a
.
dx ma2
2 2
Then
2 2
π 2 πx 2 π2
Eψ = − ψxx = √ cos = ψ.
2m 2m L 2L 2L 8mL2
2 π 2 /(8mL2 ).
Thus. E =
2.30 The wave function of a particle confined to a box of length L is
2/L sin(πx/L) in the region 0 < x < L and zero everywhere else. Cal-
culate the probability of finding the particle in the region 0 < x ≤ L/2.
We obtain
L/2
P (0 < x ≤ L/2) = ψ ∗ ψ dx
0
L/2
2 πx
= sin2 dx
L 0 L
L/2
1 2πx 1
= 1 − cos dx = .
L 0 L 2
2.31 Write the law of conservation of energy H = T + V in terms of expec-
tation values.
We write �H� = �T � + �V �.
0
2.32 Are the wave functions
1/2 1/2
1 r/a0 1 r r/(2a0 )
− a −
ψ1 = 0 e and ψ2 = 2− e
πa3 32πa3 0
= 0.
∞
Since ψ ∗1 ψ 2dτ = 0, the given two wave functions are orthogonal.
0
(b) ψ = A sin(πx/(2L)) for |x| < L and 0 for |x| > L, E = 2 π 2 /(8mL2 ).
− 2 d2 ψ 2
+ V ψ = Eψ or Vψ= ψxx + Eψ .
2m dx2 2m
Substituting the given ψ and E in the above equation we get
2 2
d
Vψ= (−x)ψ + Eψ = −ψ + x2 ψ + Eψ .
2m dx 2m
Then
2 2
ω
V = −1 + x 2
+E = x −1 +
2
.
2m 2m 2
We get
L
φ∗1 e iE1 τ /
+ φ∗2 eiE2 τ / (φ1 + φ2 ) dx = 0 .
0
L
Since φ φ dx = δ we get eiE1 τ / + eiE2 τ / = 0. That is
0 m n mn
E1 τ E1 τ E2 τ E2 τ
cos + i sin + cos + i sin =0.
∞
= (p†x ψ)∗ xψ dx
−∞
∞ ∗
= px ψx∗ ψ ∗ dx
−∞
∞ ∗
= ψ ∗ xpx ψ dx
−∞
= �xpx �∗ .
Now, �xpx + px x� = �xpx � + �px x� = �xpx � + �xpx �∗ = 2Re�xpx �. Thus
�xpx + px x� is real.
−∞
∞
= ψ A Aψ dτ
∗ n−1
−∞
∞
= α ψ ∗ An−1 ψ dτ
−∞
∞
= αn ψ ∗ ψ dτ
−∞
= αn .
∞ ∞
We find �A� = ψ ∗ Aψ dτ = α ψ ∗ ψ dτ = α. Hence, �An � = αn =
−∞ −∞
n
�A� .
√
2.37 Calculate �p2 � for ψ = e−k|x| .
x k
We obtain
∞ ∞ 2
d −k|x|
�p
x � =
2
ψ ∗ p2x ψ dx = − 2
e−k|x| e dx .
dx2
−∞ −∞
0 30
That is, N = 30/L5 . Next,
L
�E� = ψ ∗ Hψ dx
0
L 2
d2
= ψ −
0 2m dx2 ψ dx
2 L
= N2 xL − x2 dx
m 0
5 2
= .
mL2
d 2 2 i
2.39 Show that �x � = �xpx � − .
dt m m
∞
�x2 � is given by �x2 � = ψ ∗ x2 ψ dx. Then
−∞
∞
d 2 d
�x � = ψ ∗ x 2 ψ dx
dt dt −∞
∞ ∞
∂ψ ∗ ∂ψ
= x2 ψ dx + ψ ∗2x dx .
−∞ ∂t −∞ ∂t
∂ψ ∂ψ ∗
Using the Schrödinger equation for and we get
∂t ∂t
∞
d 2 1 p2xψ ∗ ∗ 2
�x � = − +Vψ x ψdx
dt i −∞ 2m
∞
1 p2
∗ 2
+ ψ x x
ψ+Vψ dx
i −∞ 2m
i =
2m
K24365_SM_Cover.indd 35 13/11/14 6:56 PM
∞
i∞
ψ ∗ p2 x2 ψ x dx
−∞ −
2m ψ ∗ x2 p2 ψ
dx . x
−∞
2
= �xpx � − .
m m
d 2 2
2.40 Show that �x2 � = �p2 � + �xF �.
x
dt2 m2 m
d 2 i
We have � x2 � = �xpx � − . Then
dt m m
d2 2 2 d
�x � = �xpx �
dt2 m dt
∞
2 d
= ψ ∗ (xpx )ψ dx
m dt −∞
2 ∞ ∂ψ ∗ 2 ∞
∂ψ
= xpx ψ dx + ψ ∗ xpx dx .
m −∞ ∂t m −∞ ∂t
∞ ∞
i 3 2i
− ψ ∗ xpx ψ dx − ψ ∗ xpx (V ψ) dx
m2 −∞ m −∞
∞
i
= ψ 2 px (px xpx ψ + xp2 ψ) − xp3 ψ dx
x x
m2 −∞
∞
2i dV
− ψ ∗ xψ −i dx .
m −∞ dx
�px � = px ψ dτ + ψ ∗ px dτ .
dt −∞ ∂t −∞ ∂t
�px � = − +Vψ px ψ dτ
dt i −∞ 2m
∞
1 p2 ψ
+ ψ ∗ p2x x
+Vψ dτ .
i −∞ 2m
That is,
∞ ∞
d 2 i 2 i 2
∗
�px � = V ψ px ψ dτ − ψ ∗ px (V ψ) dτ
dt −∞ −∞
∞ ∞
i
= − 2 ψ ∗ px V px ψ dτ + ψ ∗ p2 V ψdτ
−∞ −∞ x
∞ ∞
i i
= −2 (−i ) ψ ∗ ∇V px ψ dτ − (−i ) ψ ∗ (px ∇V )ψ dτ
−∞ −∞
∞ ∞
= 2 ψ ∗ F p x ψ dτ + ψ ∗ p x F ψdτ
−∞ −∞
�2F px + px F
=
�.
d 1
2.42 Show that �px x� �p 2
� + �xF �.
dt m x
=
= −i ψ ∗ ψ dx + ψ ∗ xpx ψ dx
−∞ −∞
∞
= −i + ψ ∗ xpx ψ dx .
−∞
Now
�px x� =
d dt
We have
∂ψ p2x ∂ψ ∗ p2x
i = ψ+Vψ , −i = ψ∗ + V ψ∗ .
∂t 2m ∂t 2m
∞ ∞
i 3 i
− ψ ∗ xpx ψ dx − ψ ∗ xpx (V ψ) dx
2m −∞ −∞
∞ ∞
i i
= ψ ∗ p2x (xpx ψ) dx − ψ ∗ xp3x ψ dx
2m −∞ 2m −∞
∞
+ ψ ∗ xψF dx .
−∞
Then
∞ ∞
d i 2 i 3
∗ ∗
�px x� = ψ px (xpx ψ) dx − ψ xpx ψ dx + �xF �
dt 2m −∞ 2m −∞
∞
i
= ψ ∗ px xp2x ψ dx + �xF �
2m −∞
∞
1
= ψ ∗ p2x ψ dx + �xF �
m −∞
1 2
= �p � + �xF � .
m x
d 2 d 2
2.43 For a free particle show that �p � = 0 and �xpx + px x� = �p2x �.
dt x dt m
d 1 d 2
�px x� = �px2 � , �p � = 0 .
dt m dt x
2.44 φ1 and φ2 are the only eigenfunctions of a system belonging to the energy
eigenvalues E0 and −E0 respectively. In a measurement of the energy
of the system, �E� is found to be E0 /2. Find the wave function of
the system.
�E� = 1 C 2 E1 +2 C 2 E2
= C12 E0 − C22 E0
= E0 C 21 − C 22 .
d e
and �p − eA� = eE0 k �p − eA� × ∇ × A.
dt m
+
1 2
∇ × A is obtained as ∇ × A = B0 k. H is (p − eA) − eE0 . Now,
2m
d
consider �x�. We obtain
dt
∞
d ∂ψ ∗ ∞
∂ψ
�x� = xψ dx + ψ∗x dx
dt −∞ ∂t ∂t
−∞
= ∞ ∞
1 1
− Hψ ∗ xψ dx + ψ ∗ xHψ dx
i −∞ i −∞
1
= �[x, H]� .
i
Next, we find
1
[x, H] = x, (p − eA) · (p − eA) + eE0
2m
1 1
= x, px2 + x, e2 A2
2m 2m
1 1
− [x, p · eA] − [x, eA · p] + [x, eE0 ]
2m 2m
1 1 1
= x, px2 − (i eAx ) − (i eAx )
2m 2m 2m
i i
= px − eAx .
m m
Therefore,
d 1 i eAx 1
�x� = px − i = m (px − eAx ) .
dt i m m
Hence,
d 1
�r� = �p − eA� .
dt m
Next,
d2 d d d
�r� = �F� = m �r� =
dt2 dt dt
�p − eA�
dt
1
= �[p − eA, H]�
i
Hence,
d e
�p − eA� = �F� = eE0 k + (p − eA) × ∇ × A .
dt m
fore,
1
ψ = √ (φ1 + φ3 ) .
2
If the energy is measured then one may get the energy as E1 with the
probability 1/2 and E3 with probability 1/2.
(ii) We obtain
1 5π 2 2
�E� = C 2 E1 + C 2 E3 = (E1 + E3 ) = .
1 3
2 2mL2
2.47 Given the normalized ground state wave function of hydrogen atom
ψ100 = 1/(πa30)1/2 e−r/a0 find the expectation value of its z-coordinate.
We obtain
∞ π 2π
1 − 2r/a0 2
�z� = e zr dr sin θdθ dφ .
πa2
0 0 0 0
= − 3 cos 2θ|0
r e 0
dr
2a0 0
= 0.
E = ψ|H|ψ
∞
= C n∗ Cn ei(En −En )t/
φ∗n Hφn dx
n n −∞
∞
= Cn Cn∗ ei(En −En )t/ φ∗n En φn dx
n n −∞
= |Cn |2 En .
n
√
2.49 Consider a system in a state ψ = (φ1 + φ2 )/ 2 where φ1 and φ2 are
APPENDIX
VENEREAL DISEASES IN THE HOMOSEXUAL
It is an old belief, shared by the homosexual themselves, that
venereal infections are extremely rare among them. If male
homosexual persons had sexual intercourse only with one
another, this assumption would be in some degree plausible. For
the principal focus of venereal infection is feminine prostitution, by
which venereal diseases are transmitted to heterosexual men. But
since these homosexual men often undertake sexual acts with
heterosexual men—apart from occasional sexual intercourse with
women—a priori there is a possibility of infection in their case, and
such infection is, in fact, observed. Above all, many male prostitutes
also indulge in intercourse with women, and thus diffuse venereal
troubles among homosexual men.
It is obvious that syphilis can be diffused among the homosexual
as easily as among the heterosexual, for syphilis is transmitted by
many varieties of contact—by kisses, other caresses, etc. But how is
it as regards gonorrhœa?
In the case of heterosexual men and women gonorrhœa is almost
exclusively transmitted by the sexual act, by the introduction of the
male penis into the female vagina. The analogous act between men
—that is to say, pæderasty, immissio penis in anum—is
unquestionably far rarer than the ordinary sexual act between men
and women; it is commonly replaced by mutual onanism, by kisses
and other caresses, and quite frequently by coitus in os. This last is
much commoner than genuine pædication. Of gonorrhœa of the
rectum produced by pædication when the active man is suffering
from gonorrhœa, we very rarely hear. But is there, in the case of
homosexual men, any possibility of gonorrhœal infection due to
coitus in os?
There can be no doubt that typical gonorrhœa of the mouth
occurs. The observations of Kuttler, Atkinson, Rosinski, Dohrn, and
Kast, have proved it.[328] Horand and Cazenave have even observed
gonorrhœal infection of the urethra as a result of oral coitus![329] A
homosexual patient told me that some years before, after coitus in
os with a man, he had for several weeks had a discharge from the
urethra, which spontaneously ceased, and therefore cannot have
been genuine gonorrhœa, but only urethritis resulting from infection
by contagious angina. In the case in question, the urethral catarrh
was certainly due to the coitus in os, since any other sources of
infection could be excluded.
On the other hand, in a second case an apparently gonorrhœal
infection of the oral cavity was transmitted from the urethra.
A homosexual man, forty-five years of age, one day allowed a heterosexual
man to perform coitus in os on him. Some days afterwards he experienced
difficulty in swallowing, was feverish, and saw in the looking-glass that the uvula
was swollen. A specialist for throat troubles diagnosed merely a catarrhal infection.
The illness became worse, and a second throat specialist detected the presence of
a purulent angina of both tonsils, ordered painting with argentamin, also vapour
baths, and an astringent gargle, whereupon the affection gradually subsided. Six
weeks later the patient had swelling and pain in the joints of the right knee and
foot; under cold compresses these swellings subsided after a fortnight. Of the
whole trouble nothing now remains.
CONTENTS OF CHAPTER XV
The suppression of venereal diseases — Organization of the campaign against
them — International Conference in Brussels — Foundation of the German
Society for the Suppression of Venereal Diseases — Three methods of
carrying on the campaign against venereal diseases.
Personal Prophylaxis against Venereal Diseases: Rôle of cleanliness — The
preputial secretion and balanitis — Importance of circumcision — Technique
of the cleansing of the genital organs before and after sexual intercourse —
Examination for disease — Dangers of repeated coitus — Special protective
measures — The condom — Varieties and technique of its use — The
instillation of solutions of silver salts — Their relative value — The inunction of
fat — Metchnikoff’s ointment for the prevention of syphilis — Antiseptic
washings — The public advertisement of protective measures — Legal
protection against venereal infection — Opinions of legal authorities on this
subject (von Liszt, von Bar, Schmölder).
The Suppression of Venereal Diseases by Medical Treatment: Favourable
conditions as regards syphilis — Mitigation of the syphilitic virus — Mercury
and its importance — A “triumph of medicine” — Methods of employing
mercury in the treatment of syphilis — Mode of action of the mercury cure —
Means for the after-treatment of syphilis — Curability of syphilis — Treatment
of gonorrhœa — Necessity for microscopical examination and the scientific
methods to be employed — The different modes of treatment — The
determination of the cure of gonorrhœa — Facilitation of the treatment of
venereal diseases for the great mass of the public — “Krankenkassen”[330] and
venereal diseases.
State Action and Public Action in the Campaign against Venereal Diseases:
Statistics of venereal troubles — Blaschko’s researches — Frequency of
venereal diseases in Denmark — Among various classes in Germany —
Prussian statistics of April 30, 1900 — Conclusions deducible from these
statistics — The different sources of infection — Prostitution the principal
source of infection — Danger of youthful prostitutes — Measures to be taken
by the State against the diffusion of diseases by prostitution — Regulation —
Criticism of this measure — Its illegality — Its uselessness and its dangers —
Favourable results of the withdrawal of “moral control” — Prostitution and
crime — Soutenage — Criticism of Lombroso’s theory of the relations between
prostitution and criminality — The brothel question — Diminution in the
number of brothels — Dangers of brothels — Brothel streets and the limitation
of prostitution to definite quarters — Proposals for the examination of the
male clientèle — Criticism of these proposals — The true way towards the
suppression of prostitution.
CHAPTER XV
The motto which I have placed at the head of this chapter on the
campaign against venereal diseases and on the attempt to suppress
them is taken from an interesting academic essay by the former
professor of medicine at Göttingen, K. F. H. Marx, who is well known
to have been the physician of Heinrich Heine during the latter’s
student life in Göttingen. The title of this essay is “The Diminution of
Diseases in Consequence of Advancing Civilization,” p. 35 (Göttingen,
1844).
The hopeful view which is here expressed by the university
professor regarding the ultimate eradication of venereal diseases
was shared at that time by the eminently practical physician
Parent-Duchatelet. He appeals, unfortunately, not to medical men
and students of social hygiene, but to the police:
“Pursue without cessation the diseases which are diffused by means of
prostitutes; take it as your goal to cause them to disappear from the list of
human troubles; do not doubt that your labours will ultimately be
crowned with success, although the task may be one that will occupy
several generations.”[331]
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