Ht trong hp ba chiu s suy bin

L L
Ngy 27 thng 7 nm 2009
Tm tt ni dung
Hin tng suy bin ca cc mc nng lng l mt hin tng
kh ph bin i vi cc h vi m. Chng ta s bc u tm hiu
hin tng ny thng qua vic kho st nng lng ca ht chuyn
ng trong khng gian ba chiu. T kt qu bi ton ht trong hp
ch nht, chng ta s tnh cc gi tr trung bnh nh v tr v ng
lng ca ht.
1 Phng trnh Schrodinger cho h mt ht trong
khng gian ba chiu
Phng trnh Schr odinger khng ph thuc thi gian cho h mt ht, trong
khng gian mt chiu c vit nh sau

H(x) = E(x) (1)

vi E l nng lng;

H l ton t Hamiltonian

H =

T
x
+

V (x) =

2
2m
d
2
dx
2
+ V (x) (2)
Trong (2), ton t

T
x
l ton t ng nng;

V (x) l ton t th nng.
Trong khng gian ba chiu, ng nng cng nh th nng ca h ph
thuc vo c ba thnh phn ta x, y, z

V = V (x, y, z) (3)

T =

T
x
+

T
y
+

T
z
=

2
2m
_

2
x
2
+

2
y
2
+

2
z
2
_
(4)
Do , phng trnh Schr odinger khng ph thuc thi gian cho h mt ht,
trong khng gian ba chiu c dng
_

2
2m
_

2
x
2
+

2
y
2
+

2
z
2
_
+ V (x, y, z)
_
(x, y, z) = E(x, y, z) (5)
1
Trong (5), ton t

2
x
2
+

2
y
2
+

2
z
2
(6)
c gi l ton t Laplacian (
2
del bnh phng). Nh vy, phng
trnh Schr odinger (5) c th c vit gn hn nh sau
_

2
2m

2
+ V (x, y, z)
_
(x, y, z) = E(x, y, z) (7)
Nu h gm n ht th ng nng ca h bng tng ng nng ca cc
ht trong h. Do , ta c

T =
n

i=1

T
i
=
n

i=1

2
2m
i

2
i
(8)
Th nng l hm ph thuc vo ta ca cc ht trong h
V = V (x
1
, y
1
, z
1
, . . . , x
n
, y
n
, z
n
) = V (q
1
, . . . , q
n
) (9)
Hm trng thi ca h cng s ph thuc vo ta ca tt c cc ht
trong h
= (x
1
, y
1
, z
1
, . . . , x
n
, y
n
, z
n
) = (q
1
, . . . , q
n
) (10)
Nh vy, i vi h nhiu ht, trong khng gian ba chiu, phng trnh
Schr odinger khng ph thuc thi gian l
_
n

i=1

2
2m
i

2
i
+ V (q
1
, . . . , q
n
)
_
(q
1
, . . . , q
n
) = E(q
1
, . . . , q
n
) (11)
V d, phng trnh Schrodinger cho mt h gm hai ht chuyn ng
v tng tc vi nhau, trong khng gian ba chiu c vit nh sau
_

2
2m
1

2
1
+

2
2m
2

2
2
+ V (q
1
, q
2
)
_
(q
1
, q
2
) = E(q
1
, q
2
)
Trong q
1
= x
1
, y
1
, z
1
v q
2
= x
2
, y
2
, z
2
l ta ca ht th nht v ht
th hai.
2 Ht trong hp ba chiu
V (x, y, z) = 0 bn trong vng
_
_
_
0 < x < a
0 < y < b
0 < z < c
V = nhng ni khc
2
Hp m chng ta s xt n l hp ch nht vi di cc cnh l a, b, v
c. H ta c chn sao cho mt trong cc nh ca hp nm ti gc ta
v cc trc x, y, z l ba trong s 12 cnh ca hp. Th nng bn trong
hp l zero; ngoi hp l v cng.
Vi iu kin nh trn, ta kt lun rng hm sng bng zero bn ngoi
hp. Bn trong hp, ton t th nng bng zero, nn phng trnh sng
Schr odinger khng ph thuc thi gian s l

2
2m
_

2
x
2
+

2
y
2
+

2
z
2
_
(x, y, z) = E(x, y, z) (12)
Gi s nghim ca phng trnh (12) c vit di dng tch ca ba
hm X(x), Y (y), v Z(z) cha cc bin s x, y, z c lp; ngha l
(x, y, z) = X(x)Y (y)Z(z) (13)
Phng php c dng gii phng trnh vi phn nh trn c gi l
phng php tch bin (seperation of variables).
Th (13) vo (12), nhng n gin ta vit X, Y, Z thay v X(x), Y (y),
Z(z), ta c

2
(XY Z)
x
2
+

2
(XY Z)
y
2
+

2
(XY Z)
z
2
=
2m

2
E(XY Z) (14)
V Y Z khng phi l hm ca x; XZ khng phi l hm ca y; XY khng
phi l hm ca z nn ta c

2
(XY Z)
x
2
= Y Z

2
X
x
2

2
(XY Z)
y
2
= XZ

2
Y
y
2

2
(XY Z)
z
2
= XY

2
Z
z
2
Do , (14) tr thnh
Y Z

2
X
x
2
+ XZ

2
Y
y
2
+ XY

2
Z
z
2
=
2m

2
E(XY Z) (15)
Chia phng trnh (15) cho XY Z, ta c
1
X
X

+
1
Y
Y

+
1
Z
Z

=
2m

2
E (16)
hay

2
2m
X

(x)
X(x)


2
2m
Y

(y)
Y (y)


2
2m
Z

(z)
Z(z)
= E (17)
3
T , ta c

2
2m
X

(x)
X(x)
= E +

2
2m
Y

(y)
Y (y)
+

2
2m
Z

(z)
Z(z)
(18)
Ta thy v tri ca phng trnh (18) hon ton khng ph thuc vo
cc bin y v z. Trong khi , v phi ca (18) hon ton khng ph thuc
vo bin x. Nh vy hai v phng trnh bng nhau th phng trnh
phi bng mt hng s. t hng s ny l E
x
, ta c
E
x
=

2
2m
X

(x)
X(x)
(19)
Lp lun tng t nh trn, ta c
E
y
=

2
2m
Y

(y)
Y (y)
; E
z
=

2
2m
Z

(x)
Z(z)
(20)
Kt hp vi (19) v (20), phng trnh (18) tr thnh
E = E
x
+ E
y
+ E
z
(21)
Ta vit li cc phng trnh (19) v (20) nh sau
X

(x) +
2m

2
E
x
X(x) = 0 (22)
Y

(y) +
2m

2
E
y
Y (y) = 0 (23)
Z

(z) +
2m

2
E
z
Z(z) = 0 (24)
Tm li, chng ta chuyn mt phng trnh vi phn ring phn vi ba
bin thnh ba phng trnh vi phn ch cha mt bin. Ta thy (22) chnh
l phng trnh Schr odinger cho ht trong hp mt chiu vi th nng trong
hp V (x) = 0 v chiu di l l = a. Nh vy, nghim ca (22) l
X(x) =
_
2
a
sin
_
n
x
x
a
_
(25)
E
x
=
n
2
x
h
2
8ma
2
(n
x
= 1, 2, 3, . . .) (26)
Tng t, ta c
Y (y) =
_
2
b
sin
_
n
y
y
b
_
(27)
E
y
=
n
2
y
h
2
8mb
2
(n
y
= 1, 2, 3, . . .) (28)
4
v
Z(z) =
_
2
c
sin
_
n
z
z
c
_
(29)
E
z
=
n
2
z
h
2
8mc
2
(n
z
= 1, 2, 3, . . .) (30)
Nh vy, nng lng ca h
E = E
x
+ E
y
+ E
z
=
h
2
8m
_
n
2
x
a
2
+
n
2
y
b
2
+
n
2
z
c
2
_
(31)
Hm sng ca ht trong hp ch nht
(x, y, z) = X(x)Y (y)Z(z)
(x, y, z) =
_
8
abc
sin(
n
x
x
a
) sin(
n
y
y
b
) sin(
n
z
z
c
) (32)
Trong , a, b, c l di ca cc cnh theo cc trc x, y, z tng ng. Hm
sng c ba s lng t n
x
, n
y
v n
z
. Chng bin i mt cch c lp vi
nhau.
Hm sng c dng
(x, y, z) = X(x)Y (y)Z(z)
c chun ha nh sau
_ _ _

(x, y, z)

2
dxdydz =
_ _ _

X(x)Y (y)Z(z)

2
dxdydz
=
_

X(x)

2
dx
_

Y (y)

2
dy
_

Z(z)

2
dz
= 1
hay
_

X(x)

2
dx =
_

Y (y)

2
dy =
_

Z(z)

2
dz = 1 (33)
3 S suy bin
Xt hp c dng hnh lp phng, a = b = c. Khi , cc mc nng lng
c xc nh bi
E =
h
2
8ma
2
(n
2
x
+ n
2
y
+ n
2
z
) (34)
Nng lng thp nht hay nng lng im khng ca ht, ng vi trng
thi n
x
= n
y
= n
z
= 1, l
E
111
= 3
h
2
8ma
2
5
bng ba ln nng lng ca ht trong hp mt chiu c dng di. Cc
mc nng lng tip theo thu c khi tng dn cc gi tr n
x
, n
y
, n
z
. V
d, khi tng mt s lng t ln 2, gia nguyn hai s lng t cn li l 1,
ta s c 3 gi tr E
211
, E
121
, E
112
. Vi b ba s lng t (1, 1, 2) th
n
2
x
+ n
2
y
+ n
2
z
= 6
Do
E
211
= E
121
= E
112
= 6
h
2
8ma
2
Tng t, vi b ba s lng t (1, 1, 3) th
E
311
= E
131
= E
113
= 11
h
2
8ma
2
n
2
x
+ n
2
y
+ n
2
z
n
x
n
y
n
z
E Bc suy bin
3 111 3(h
2
/8ma
2
) 1
6 211 121 112 6(h
2
/8ma
2
) 3
9 221 212 122 9(h
2
/8ma
2
) 3
11 311 131 113 11(h
2
/8ma
2
) 3
12 222 12(h
2
/8ma
2
) 1
14 321 312 231 213 132 123 14(h
2
/8ma
2
) 6
Bng 1.1: Mt s mc nng lng thp nht ca ht trong hp
6
E
111
121 112 211
122 212 221
Hnh 1.1: Mt s mc nng lng thp nht ca ht trong hp
Chng ta thy c nhng trng thi m nng lng ca ht bng nhau
mc d s lng t khc nhau. V d, ng vi gi tr
n
2
x
+ n
2
y
+ n
2
z
= 6 E = 6(h
2
/8ma
2
)
c n ba trng thi l
n
x
n
y
n
z
Trng thi
1 1 2
112
1 2 1
121
2 1 1
211
6
Nh vy, ng vi mc nng lng E = 6(h
2
/8ma
2
), ht trong hp lp
phng c m t bi ba hm sng

112
=
_
8
a
3
sin(
x
a
) sin(
y
a
) sin(
2z
a
)

121
=
_
8
a
3
sin(
x
a
) sin(
2y
a
) sin(
z
a
)

211
=
_
8
a
3
sin(
2x
a
) sin(
y
a
) sin(
z
a
)
Ba hm sng
211
,
121
,
112
m t ba trng thi khc nhau ca h vi cng
mc nng lng. Khi hai hay nhiu hm sng tng ng vi nhng tng thi
c cng c tr nng lng th c tr ny c gi l suy bin (degenerate).
Bc suy bin ca mt mc nng lng l s trng thi m mc nng lng
c. Trong v d trn ta c suy bin bc ba: c ba trng thi cng mc
nng lng E = 6(h
2
/8ma
2
).
4 S chng cht cc trng thi suy bin
Xt mt trng thi suy bin bc n, ngha l c n hm sng c lp
1
,
2
,

3
, . . .,
n
cng mc nng lng E. Ta c

H
1
= E
1
;

H
2
= E
2
; . . .

H
n
= E
n
(35)
Theo nguyn l chng cht, nu
1
,
2
,
3
, ...,
n
l nhng trng thi ca
mt h th trng thi c xc nh bi
= c
1

1
+ c
2

2
+ + c
n

n
(36)
cng l mt trng thi ca h. Tht vy, t (36), ta c

H =

H(c
1

1
+ c
2

2
+ + c
n

n
) (37)
Ton t nng lng

H l ton t tuyn tnh. Do

H(c
1

1
+ c
2

2
+ + c
n

n
) = c
1

H
1
+ c
2

H
2
+ + c
n

H
n
(38)
Th (35) vo (38), ta c

H(c
1

1
+ c
2

2
+ + c
n

n
) = c
1
E
1
+ c
2
E
2
+ + c
n
E
n
= E(c
1

1
+ c
2

2
+ + c
n

n
)
v = c
1

1
+ c
2

2
+ + c
n

n
nn phng trnh trn tr thnh

H = E (39)
7
T kt qu trn, ta thy hm t hp tuyn tnh cng l mt c hm ca
ton t Hamiltonian vi cng c tr nng lng E. Do , n cng l mt
trng thi ca h.
Nu h suy bin bc hai th ta ch c mt trng thi t hp tuyn tnh
= c
1

1
+ c
2

2
Khi bc suy bin ln hn hai, s c rt nhiu trng thi t hp tuyn tnh
c to ra. V d, vi trng hp suy bin bc ba, ta c cc trng thi t
hp tuyn tnh nh sau

12
= c
1

1
+ c
2

13
= c
1

1
+ c
3

23
= c
2

2
+ c
3

123
= c
1

1
+ c
2

2
+ c
3

3
Cc trng thi ny u c cng mc nng lng.
5 Gi tr trung bnh
Tin hnh n php th. Gi s B l i lng ngu nhin nhn cc gi tr
c th b
1
, b
2
, . . . , b
n
vi s ln nhn l k
1
, k
2
, . . . , k
n
. Gi tr trung bnh ca
i lng ngu nhin B trong n php th l

b = b =
1
n
(k
1
b
1
+ b
2
x
2
+ + b
n
x
n
) =

i
k
i
n
b
i
=

i
f
i
b
i
(40)
vi f
i
=
k
i
n
l tn sut B nhn gi tr b
i
. V d, khi tin hnh kho st
im thi ca 9 sinh vin, ta c kt qu nh sau 0,20,20,60,60,80,80,80,100.
im trung bnh trong trng hp ny l
1
n

i
k
i
b
i
=
1
9
{1(0) + 2(20) + 2(60) + 3(80) + 1(100)} = 56
Khi n ln th t s
k
i
n
chnh l xc sut quan st thy gi tr b
i
, k
hiu l P
i
, ta c
b =

i
P
i
b
i
(41)
v gi tr trung bnh b c gi l gi tr k vng.
By gi, gi s chng ta mun xc nh v tr ca mt ht ang trng
thi (x). Theo Born,

(x)

2
l xc sut tm thy ht ti v tr x. iu ny
c ngha l cc php o ta x khng cho mt kt qu duy nht. Nu ta
8
thc hin php o nhiu ln th ta s thu c nhiu gi tr khc nhau. Do
, c th ta s phi tnh gi tr trung bnh x cho nhng php o ny. Ta
x c gi tr lin tc, v xc sut tm thy ht l hm mt xc sut

2
nn gi tr trung bnh x c tnh nh sau
x =
_
+

2
dx =
_
+

xdx (42)
y, chng ta xem gi tr trung bnh l gi tr k vng. Theo l thuyt xc
sut thng k, gi s X l i lng ngu nhin lin tc c hm mt xc
sut f(x). K vng ca i lng ngu nhin X c xc nh bi
E
X
=
_
+

xf(x)dx
Tng qut, gi tr trung bnh ca mt thuc tnh B c xc nh bi
B =
_

Bdx (43)
Khi p dng vo c hc lng t th thuc tnh B s c thay th bng
ton t

B ca thuc tnh . Nh vy (43) tr thnh
B =
_

Bdx (44)
Trong trng hp c bit, nu l mt c hm ca

B vi c tr ;
ngha l

B =
th ta c
B =
_

Bdx =
_

dx =
_

dx = (45)
v
_

dx = 1
do hm c chun ha. Nh vy, gi tr trung bnh cng chnh l c
tr. Ni cch khc, c tr ca ton t

B l kt qu duy nht ta thu c
khi thc hin php o thuc tnh B c m t bi

B.
V d: Tm x v p
x
cho ht trong hp ch nht, trng thi c bn.
Ta c
x =
_
a
0
_
b
0
_
c
0

(x, y, z) x(x, y, z)dxdydz

9
Vi (x, y, z) = X(x)Y (y)Z(z) v x = x, ta c
x =
_
a
0
_
b
0
_
c
0
X

Y

Z

xXY Zdxdydz
=
_
a
0
X

xXdx
_
b
0
Y

Y dy
_
c
0
Z

Zdz
=
_
a
0
X

xXdx
v
_
b
0
Y

Y dy =
_
c
0
Z

Zdz = 1
Do
x =
2
a
_
a
0
xsin
2
_
x
a
_
=
a
2
Tng t, ta c
p
x
=
_
a
0
_
b
0
_
c
0
X

Y

Z

p
x
XY Zdxdydz
=
_
a
0
X

p
x
Xdx
_
b
0
Y

Y dy
_
c
0
Z

Zdz
=
_
a
0
X

p
x
Xdx
vi p
x
= i
d
dx
, ta c
p
x
= i
_
a
0
X

(x)
d
dx
X(x)dx = i
_
a
0
X(x)X

(x)dx
v X(x) =
_
2
a
sin
_
x
a
_
l hm thc nn X

(x) = X(x).
p dng cng thc tnh tch phn tng phn, t
u = X(x) ; dv = X

(x)dx du = X

(x)dx ; v = X(x)
Ta c
_
a
0
X(x)X

(x)dx = X
2
(x)

a
0

_
a
0
X(x)X

(x)dx

_
a
0
X(x)X

(x)dx =
1
2
X
2
(x)

a
0
= 0
V X(0) = X(a) = 0. Nh vy
p
x
= i
_
a
0
X(x)X

(x)dx = 0
10
Bi tp
1. Vit phng trnh Schr odinger cho nguyn t He gm mt ht nhn v
hai electron. Xem ht nhn c c nh (ng yn) ti gc ta . Cho
bit cng thc tnh th nng tng tc gia cc ht mang in l
V
ij
= k
q
i
q
j
r
2
ij
Trong , k l hng s; q
i
, q
j
l in tch ca cc ht mang in; r
ij
l
khong cch gia i v j.
2. Gii phng trnh sau theo phng php tch bin s

2
U(x, y)
x
2

U(x, y)
y
= 0
Vi
U(x, y) = X(x)Y (y)
3. Trong c hc lng t th khi nim trng thi v mc nng lng l
khng ging nhau. Gi s mt ht khi lng m trong hp lp phng vi
di mi cnh l a c cc mc nng lng E < 20

2
8ma
2
. Nh vy, c tt
c bao nhiu trng thi ng v bao nhiu mc nng lng tha mn iu
kin trn?
4. Tnh cc gi tr trung bnh x
2
, x
2
, p
2
x
v p
x

2
cho ht trng thi
c bn trong hp hnh ch nht. T tnh
xp
x
=
_
x
2
x
2

_
p
2
x
p
x

2
So snh kt qu xp
x
vi
h
2
.
Cho cng thc tnh tch phn
_
xsin
2
(kx)dx =
x
2
4

x
4k
sin(2kx)
1
8k
2
cos(2kx)
_
x
2
sin
2
(kx)dx =
x
3
6

_
x
2
4k

1
8k
3
_
sin(2kx)
x
4k
2
cos(2kx)
11