1

Chuong 4 NGUYEN TU
Ngay khi va mi ra i ly thuyet lng t a
c ng dung e giai quyet bai toan nguyen t, la
lnh vc ma ly thuyet co ien (c hoc, ien t hoc)
khong giai thch c.
Trong chng nay chung ta se khao sat
phng trnh Schroedinger cho electron trong
nguyen t; xem xet cac ket qua chnh nhan c khi
giai phng trnh nay; rut ra nhng ket luan va so
sanh vi ket qua thc nghiem. e n gian, chung
ta se ch xet trng hp nguyen t mot electron.
2
Nguyn t v quang ph nguyn t
Nguyn t
Khi nim Hy Lp v nguyn t
Vo nm 440 BC, Leucippus pht biu u tin v khi nim
nguyn t v c, Democritus (c460-371 BC) pht trin
Cc im cn ch ca thuyt nguyn t.
Tt c cc vt cht c to bi nguyn t, m qu nh c
th nhn thy. Nhng nguyn t ny khng th phn chia thnh
nhng phn nh hn.
Gia cc nguyn t l khong trng.
Nguyn t rn tuyt i.
Cc nguyn t ng nht v khng c cu trc bn trong.
Cc nguyn t khc nhau kch thc, hnh dng v khi
lng.
3
Nguyn t v quang ph nguyn t
Aristotle (384-322 BC)
John Dalton 1803-1807
Tt c cc vt cht c to t ht rt nh gi l
nguyn t
Tt c cc nguyn t ca nguyn t xc nh c
cng tnh cht ha hc c quy nh bi nguyn
t
Cc nguyn t c th thay i con ng m
chng kt hp nhng khng th c to ra hoc
ph v trong phn ng ha hc.
4
5
QUANG PH NGUYN T HIDRO
Quang ph nguyn t
Khi phng in lin tc vo trong hyro di p sut thp
th thu c quang ph vch n gin.
Quang ph vch hydro cng c ba vng:
Vng quang ph nhn thy c 4 vch r l dy Balmer
(J.Balmer 1825-1891, ngi Thu S).
Vng t ngoi v vng hng ngoi ( xem hnh )
Cng xa vch H v pha c bc sng ngn khong
cch gia 2 vch k nhau cng b dn nn nhng vch
cui dy nm st nhau kh trng thy. Trong quang ph
hyro ngoi dy Balmer cn c 4 dy na:
Dy Laiman trong vng t ngoi v 3 dy nm trong
vng hng ngoi l Paschen, Brackett v Pfund.
6
Ph nguyn t Hydro
The McGraw-Hill Companies. Permission required for reproduction or display
7
Phng trnh Schrodinger
Mc tiu: Gii phng trnh Schrodinger tm ra hm
, xc nh trng thi ca ht vi m

M
M

i
i

ng
ng
v
v

i
i
m
m

t
t
ORBITAL
ORBITAL

v
v

ng
ng
khng
khng
gian
gian
t
t

m
m
th
th

y
y
electron
electron
.
.

kh
kh
ng
ng
m
m
t
t

ch
ch

nh
nh
x
x

c
c
v
v

tr
tr

c
c

a
a
electron.
electron.

2 2
cho
cho
bi
bi

t
t
x
x

c
c
su
su

t
t
t
t

m
m
th
th

y
y
electron
electron
t
t

i
i
m
m

t
t
v
v

tr
tr

x
x

c
c

nh
nh
.
.
8
HM RING & TR RING TON T L
DNG TON T :
] P

. x . r

[ L

G
G
G
=
z
i
y
i
x
i
z

z y x

= = =
)
y
z
z
y ( i }
y
. z i (
z
y i L

= = = =
Ta lu cc h thc khng giao hon:
[ ]
z y x
L

i L

, L

= =
[ ]
x z y
L

i L

, L

= =
[ ]
y x z
L

i L

, L

= =
v cc h thc giao han:
[ ] 0 L

, L

x
2
=
[ ] 0 L

, L

y
2
=
[ ] 0 L

, L

z
2
=
Kt lun cc thnh phn ca L l
khng xc nh chnh xc ng thi.
Cc ton t KHNG cng hm
ring
Kt lun cc thnh phn ca L v L
2
l xc nh chnh xc ng thi.
Cc ton t cng hm ring
9
TON T MMEN XUNG LNG TRONG H TD CU
H TA CU

X
y
Z
O
x = r sin .cos r
2 =
x
2
+y
2
+z
2
y = r sin .sin tg= y/x
z = r cos cos = z/r
CC THNH PHN TON T MMEN
XUNG LNG TRONG H TA CU
) cos g cot (sin i L

= = ) sin g cot (cos i L

= =

= = i L

z
)]
sin
1
) (sin
sin
1
[ L

2
2
2
2 2

= =
2
2
2 2 2
2
2
sin r
1
) (sin
sin r
1
)
r
r (
r
.
r
1

=
10
3. MC CH L XC NH HM RING CHO L
Z
DNG PHNG TRNH C BN

= = i L

z
z z
z
U . L
U
i =

=
Chuyn v
= d .
iL
U
dU
z
z
z
=
)
. iLz
exp( . A U
z
=

=
l hmtun hon chu k l 2pi, nn mbo s n tr :
) 2 ( U ) ( U
z z
+ =
)
2 . iLz
exp( ).
. iLz
exp( A )
. iLz
exp( A
= = =

=

1 )
2 Lz
cos( )
2 . Lz
.( sin . i )
2 . iLz
exp( =

= = =
Suy ra:
) 2 m cos( 1 )
2 . Lz
.( cos = =

=
=

2 m
2 Lz
=
=
=
m L m
L
z
z
= =
Tr ring Lz bng mt s nguyn ln Hs Planck, b lng t
ha, m phi gii ni v phi nh hn mt gii hn m
m
no .
11
4.1. NGUYEN T MOT ELECTRON
Xet he gom mot hat nhan co ien tch Ze (Z
= 1,2,..) ng yen va mot electron khoi
lng m
e
chuyen ong chung quanh nhan.
The nang cua electron tai khoang cach r t
hat nhan la (trng Coulomb)
U = Ze2/4
o
r.
Phng trnh Schroedinger
+ + =
2
4
0
2
2
m
E
Ze
r
e
o
=
( ) .

12
ay la bai toan 3 chieu, nhng co tnh oi
xng cau, nen tot nhat la dung he toa o
cau. Bang cach viet dang cua toan t
Laplace theo toa o cau ta c phng
trnh Schroedinger co dang
( )
2
2
2 2 2 2 2 2
1 1 1 2m
r sin E U(r) 0
r r r r sin r sin

+ + + =



=
( )
2 2
2 2 2 2
1 1 2m

r L E U(r) 0
r r r r

+ =



= =
Dng phng php phn ly bin s:
(r, , ) R(r).Y( , ) =
13
Sau khi thay vo PT schrodinger:
V hai phng trnh theo hai bin s khc nhau
chng ch bng nhau khi u bng mt hng s.
PT bn v tri ch gii c vi K Lagrange:
=

+ + ]
Y
sin Y
1
)
Y
(sin
sin Y
1
[ )
r 4
ze
E (
m 2
)
dr
dR
r (
dr
d
R
1
2
2
2
0
2
2
2
=
) 1 ( )
r 4
ze
E (
m 2
)
dr
dR
r (
dr
d
R
1
0
2
2
2
+ = =

+ + A A
=
) ( ). ( D ) , ( Y =
Tip tc phn ly hm bn phi theo hai bin s khc nhau
2
2
2
2
m
) ( 1
sin ) 1 ( )
D
(sin sin
) ( D
1
=

= + +

A A
Thay vo PT schrodinger cho ta kt qu v phi
) im exp( e ) (
im
= =

14
LI GII CHO HM D() : C dng
) (cos P
m

A
l hmLegendre lin h vi a thc Legendre theo CT:
) x ( P
dx
d
) x 1 ( ) x ( P
m
2 / m
2 m
A A

=
trong a thc Lagendre hng th l: A
A
A
A
A
A
) 1 x (
dx
d
! 2
1
) x ( P
2

=
Quan h gia m v : A
m=0, 1, 2, 3. . . ( m - ) A
A
Bi tp: Tnh
1 ) x ( P
0
=
= ) x ( P
1
x ) 1 x (
dx
d
2
1
) x ( P
2
1
=

=
) 1 x 3 (
2
1
) 1 x (
dx
d
2 . 4
1
) x ( P
2 2 2
2
2
=

=
= ) x ( P
2
15
Thay a thc Lagendre vo hm Lagendre
) x ( P
dx
d
) x 1 ( ) x ( P
m
2 / m
2 m
A A

=
Bi tp: Tnh
= ) x ( P
0
0
1 ) x ( P
0
0
=
= ) x ( P
0
1
x ) x ( P ) x ( P
1
0
1
= =
1 ) x ( P
0
= x ) x ( P
1
=
) 1 x 3 (
2
1
) x ( P
2
2
=
=

) x ( P
1
1
[ ]
2 2 / 1 2
x 1 x
dx
d
) x 1 ( =

) x ( P
1
2
2 2 2 / 1 2
x 1 x 3 ) 1 x 3 (
2
1
dx
d
) x 1 ( =

= ) x ( P
0
2
2 2
) 1 x 3 (
2
1

) x ( P
2
2
) x 1 ( 3 ) 1 x 3 (
2
1
dx
d
) x 1 (
2 2
2
2
2
=

16
2. Chuyn sang bin cos v sau khi chun ha
= sin ) (cos P
1
1
= cos ) (cos P
0
1
=
2 2
2
sin 3 ) (cos P
= cos sin 3 ) (cos P
1
2
) 1 cos 3 (
2
1
) (cos P
2 0
2
=
) cos 1 ( sin 15 ) (cos P
2 3
3
=
= cos sin 15 ) (cos P
2 2
3
1 ) (cos P
0
0
=
2 / 1
0
0
4
1
) im exp( ) (cos D ) , (cos Y

= =
( ) = cos 4 / 3 ) , (cos Y
2 / 1
0
1
( )

=
i
2 / 1
1
1
e . sin 8 / 3 ) , (cos Y
( ) ) 1 cos 3 ( 16 / 5 ) (cos Y
2
2 / 1
0
2
=
( )

=
i
2 / 1
1
2
e cos sin 8 / 15 ) , (cos Y
( )

=
i 2 2
2 / 1
2
2
e sin 32 / 15 ) , (cos Y

=
i 2 2 2
3
e cos sin 15 ) , (cos Y

=
i 3 2 3
3
e ) cos 1 ( sin 15 ) , (cos Y
17
3. Li gii cho nghim R(r) ph thuc hai ch s:
) r ( R R
, n A
=
n l lng t chnh, l lng t qu o v m l lng t
t. Chng b chi phi bi qui lut :
A
n =1, 2, 3. . .
= 0, 1, 2, 3,. . , n-1 ( < n )
A
A
S m
H G F D P S TT
P O N M L K n (mc)
6 5 4 3 2 1 0 Tr
A
18
D. Di y l mt vi dng c th Tng qut:
)
a
r
exp( )
a
1
( 2 R
2
3
0 , 1
=
)
a 2
r
exp( ]
a 2
r
1 [ )
a
1
(
2
1
R
2
3
0 , 2
=
)
a 2
r
exp( )
a
r
( )
a
1
(
24
1
R
2
3
1 , 2
=
)
a 3
r
exp( ]
a
r
27
2
a 3
r 2
1 [ )
a
1
(
27
2
R
2
2
3
0 , 3

+ =
)
a 3
r
exp(
a
r
]
a 6
r
1 [ )
a
1
(
6 27
8
R
2
2
3
1 , 3

=
m 10 . 529 , 0
e m
4
a
10
2
e
2
0
=

=
=
A l bn knh qu o Bohr c dng
1 z if
e Zm
4
a
2
e
2
0

=
=
) ,. ( Y ). r ( AR ) z , y , x (
m , , n m , , n
=
A A A
)
a
r
exp( )
a
1
( 2 . 4 Y . AR
2
3
0 , 0 0 , 1 0 , 0 , 1
= =
19
KT QU V NNG LNG CA NT HYDROGEN
Rh
n
Z
n
E
) 4 (
e
2
m
n
Z
E
2
2
2
1
2
0
2
2
e
2
2
n
= =

=
=
1 15
3 2
0
4
e
s 10 . 27 , 3
) 4 ( 4
e m
R

=

=
=
R l hng s Ritber:
KT LUN QUAN TRNG
1- Mc E b lng t ha, c gi tr m
2- Ph thuc vo n, tng ln khi n tng
3- Cc i l gi tr zero. Cc tiu l E
1
4- Nng lng ion ha - E
1
=
5- S trng thi thay i theo mc n
Mi gi tr n c n
2
s trng thi khc nhau
18
2,185.10 J 13, 6eV

=
20
IV GII THCH QUANG PH H
2
1. Khi cung cp nng lng electron nhn nng lng v
chuyn mc kch thch mc E
n
. Electron (10
-8
s) n tr
v mc thp E
n
(E
n
> E
n
)v bc x in t.
n' n
2 2
1 1
E E Rh[ ]
n n '
=
Cho n=1. Ta c dy ph Lymann
n' 1
2
1 1
E E Rh[ ] n ' 2, 3, 4, 5, 6
1 n '
= =
Cho n=2. Ta c dy ph Panme
Kh kin
n' 2
2
1 1
E E Rh[ ] n ' 3, 4, 5, 6
4 n '
= =
Cho n=3. Ta c dy ph Passel
n' 3
2
1 1
E E Rh[ ] j 4, 5, 6
9 n '
= =
Cho n=4. Ta c dy ph Bracket
n' 4
2
1 1
E E Rh[ ] n ' 5, 6
16 n '
= =
21
So trang thai co cung mc nang lng
Vay ng vi mot gia tr n, xac nh mot mc
nang lng E
n
, co the co: ham trang
thai khac nhau. So ham trang thai khac nhau
nay c goi la bac suy bien cua mc nang
lng E
n
.
e phan biet cac trang thai khac nhau nay,
ngi ta goi ten trang thai co l = 0 la trang
thai s; l = 1 la trang thai p; l = 2 la trang thai
d; l=3 la trang thai f sau o lan lt theo th
t ch cai g,h,
n 1
2
l 0
(2l 1) n

=
+ =

22
Xc sut tmthy electron
Da vo tnh cht ca cc mc nng lng v
trng thi tc l ph thuc vo hm R(r).
0 m , 0 = = A
1 m , 1 = = A
0 m , 1 = = A
1 m , 1 = = A
2 m , 2 = = A
1 m , 2 = = A
0 m , 2 = = A
1 m , 2 = = A
2 m , 2 = = A
23
Cu tho, nhu khi dion tu o trang thai th
mat do xac suat tm hat o khoang cach r Ia.
3
2
2 2
10 10 0
1
(r) R (r) r 4 exp( 2r / a ) r
a

= =


100 10 00
R Y =
24
Moment ong lng qu ao
Hnh chieu cua moment qu ao tren mot
phng Oz nao o dien at bang toan t ,
tr rieng c xac nh bi:
2 2
n,l,m n,l,m

L (r, , ) l(l 1) (r, , ) = + =

L l(l 1) (l 0,1, 2, 3,..., n 1) = + = =
z

L
l
l l
n,l,m
z n,l,m l n,l,m
(r, , )

L (r, , ) i m (r, , )

= =

= =
z l
L m = =
su luong iu hoo khong gion.
25
Cac gia tri cho phop cua Lz
Trong co ien, ta a co he thc lien he gia moment t va moment goc qu ao
z l
e e e
e e e

L l(l 1); m
2m 2m 2m

= = + =
= =
28 9
B
e
e
9, 27.10 J / Gauss 5, 79.10 eV / Gauss
2m

= = =
=
z l
m =
So lng t m
l
bay gi ac trng cho o ln cua moment t,
nen c goi la so lng t t.
26
Hieu ng Zeemann n gian
Nguyen t at trong t trng eu, th moment t qu ao se
tng tac vi t trng ngoai, nhan them nang lng.
Hien tng tach vach pho di tac dung cua t trng ngoai
eu, c goi la hieu ng Zeemann n gian.
1 1
2
0 ; 0 ; 1
E m
m
B e
E E
m l n
l
e
total
l
= + =
= = =
=

+ + =
= = =
1
1
0
2
1 , 0 ; 1 , 0 ; 2
2
e
total
l
m
B e
E E
m l n
=
27
Spin cua ien t
Chieu chum nguyen t hydro trang thai c ban 1s
qua khe A roi cho truyen qua mot t trng ngoai
manh va khong eu, co cng o B(z). Phng Oz
la phng vuong goc vi phng ti ban au cua
chum nguyen t
28
Cia thiot vo spin
Nam 1925, Uhlenbeck va Goudsmit cho rang,
ngoai moment t qu ao a biet, ien t con co
moment t rieng goi la moment spin , ky hieu .
Moment t qu ao lien he mat thiet vi moment
ong lng qu ao nen moment t rieng cung co
lien he tng ng vi mot moment ong lng
rieng , goi la SPIN, ky hieu .
Vect spin co tnh chat giong nh vect moment
goc qu ao, tuan theo cac qui tac lng t giong
nh :
s

G
S
G
z s
S s(s 1) , S m = + =
G
= =
29
Momcnt dong luong toan phan va momcnt
tu toan phan
Ngoai moment qu ao, ien t con co moment
spin nen moment ong lng toan phan la tong cua
hai moment:
Vect moment t toan phan cung la tong moment
t qu ao va moment t spin:

J L S = +
z j
j
J J j( j 1) , J m
1
j l va` m (0, 1, 2,...., j)
2
= = + =
= =
G
= =
L S
e
e


(L 2S)
2m
= + = +
30
Hieu ng Zeemann d thng
(co hieu ng cua spin)
Khi at nguyen t trong t trng eu, tng
oi nho, ien t nhan them nang lng do
tng tac gia moment t cua ien t (co ke
ti hieu ng spin) vi t trng ngoai B.
Neu chon truc Oz trung vi chieu vect t
trng B, th o bien thien nang lng se la:
31
III. QUANG PH NHM KIM LOI KIM
QUI C V BIU DIN MC NNG LNG
nX E
, n
=
A
S 1 E
0 , 1
=
D 3 E
2 , 3
=
Tun theo s chn lc: v chia 4 loi
1 = A
1- Quang ph chnh :
2- Quang ph ph 1:
3- Quang ph ph 2:
4- Quang ph ph b chnh:
n m ) nS mP ( : S & 1 > = A
n m ) nP mD ( : P & 1 > = A
n m ) nP mS ( : P & 1 > = A
n m
nD mP
nD mF
: D & 1 >

= A
32
5G
5F
5D
5p
5s
4F
4D
4p
4s
3D
3p
3s
2p
2s
1s
Bi tp: Tm cc vch ph
QP Chnh QP Ph 1 QP Ph 2 QP B chnh
n m ) nS mP ( >
nP mD nP mS

nD mP
nD mF
33
Y ngha cac so lng t
Y Y ngh ngh a a ca ca c c so so l l ng ng t t
So lng t chnh n. Dung e xac nh E cua e, n nhan cac gia
tr nguyen dng 1, 2, 3 , n cang ln th E e cang cao, kch thc
orbital ngt cang ln kch thc cua cac am may e.
4 3 2 1 Chu ky
N M L K Lp
4 3 2 1 n
Vay cac electron co cung mot gia tr n tao thanh nhng AO co
kch thc gan bang nhau trong nguyen t c goi la lp orbital,
hay lp lng t.
So lng t phu l nhan cac gia tr nguyen dng t 0 (n-1)
ngha la n gia tr dung e xac nh hnh dang va ten orbital ngt.
Vi nhng ngt nhieu e, E cua e con phu thuoc vao gia tr l.
Nhng e co cung gia tr l lap nen mot phan lp va co E nh nhau
34
Y ngha cac so lng t
Y Y ngh ngh a a ca ca c c so so l l ng ng t t
Trong nhng ngt nhieu e, E cua e cung mot lp khong phai
hoan toan giong nhau ma co khac nhau chut t va phu thuoc vao so
lng t l.
f d p s Phan lp
3 2 1 0 l
mot gia tr xac nh cua so lng t chnh n th cac electron s
co nang lng nho nhat, sau o en cac electron p, d, va f do o
hnh dang cua chung cung khac nhau.
35
Y ngha cac so lng t
Y Y ngh ngh a a ca ca c c so so l l ng ng t t
36
Y ngha cac so lng t
Y Y ngh ngh a a ca ca c c so so l l ng ng t t
37
Y ngha cac so lng t
Y Y ngh ngh a a ca ca c c so so l l ng ng t t
38
39
40
Y ngha cac so lng t
Y Y ngh ngh a a ca ca c c so so l l ng ng t t
41
Y ngha cac so lng t
Y Y ngh ngh a a ca ca c c so so l l ng ng t t
So lng t t m
l
ac trng cho s nh hng cac
orbital ngt trong t trng va quyet nh so orbital co
trong mot phan lp, nhan cac gia tr t l + l ke ca
gia tr 0
V du: l = 0:
m co 1 gia tr m = 0 tc la 1 orbitan s
l = 1:
m co 3 gia tr la m = -1, 0 ,+1 tc la 3 orbitan p: p
x
, p
y
va p
z
l = 2:
m co 5 gia tr la m = -2, -1, 0, +1, +2 tc la 5 orbitan d:
d
xy
, d
xz
, d
yz
, d
z2
va d
x2-y2
va co hnh dang sau:
42
Y ngha cac so lng t
Y Y ngh ngh a a ca ca c c so so l l ng ng t t
So lng t spin electron m
s
ac trng cho s t quay cua e xung
quanh truc cua mnh theo chieu thuan hay chieu nghch vi chieu
quay kim ong ho va nhan mot trong hai gia tr t +1/2 -1/2
43
To To m m la la i i
Bon so lng t n, l, m
l
, m
s
xac nh hoan toan
trang thai cua electron trong nguyen t.
2
6
10
14
+1/2 , -1/2
0
-1, 0, +1
-2, -1, 0, +1, +2
-3, -2, -1, 0, +1, +2,
+3
4s
4p
4d
4f
0
1
2
3
4
2
6
10
+1/2 , -1/2
0
-1, 0, +1
-2, -1, 0, +1, +2
3s
3p
3d
0
1
2
3
2
6
+1/2 , -1/2 0
-1, 0, +1
2s
2p
0
1
2
2
+1/2 , -1/2
0
1s 0 1
e toi
a
So orbital ngt m
s
m
l
Orbital
l
n
44
BANG PHAN LOAI TUAN HOAN
Da vao c hoc lng t, ta co the giai thch c
s phan bo ien t trong cac nguyen to, va do o
hieu c s ton tai cua bang phan loai tuan hoan
do Mendeleev thiet lap t nam 1869.
e sap xep ien t trong nguyen t, c lng t
dung hai nguyen ly:
Nguyen ly loai tr Pauli:
moi trang thai lng t xac nh bi bon so
lng t ( n, l, m
l
, m
s
) ch co the co toi a mot
ien t.
Nguyen ly cc tieu nang lng:
He ben vng nhat khi nang lng cua he toi thieu.
45
Quy tac Kleshkowski
Khi ien tch hat nhan tang, cac e se chiem cac mc E co tong
so (n + l) ln dan.
oi vi cac phan lp co (n + l) bang nhau th e se chiem vao cac
phan lp co tr so n nho trc roi ti phan lp co n ln sau.
Chu ky 1 1s
Chu ky 2 2s 2p
Chu ky 3 3s 3p 3d
Chu ky 4 4s 4p 4d 4f
Chu ky 5 5s 5p 5d 5f
Chu ky 6 6s 6p 6d 6f
Chu ky 7 7s 7p 7d 7f
46
Quy tac Kleshkowski vi nhng ngto gto thuo thuo c c phan phan nho nho m m phu phu
Nhom 1: ns
2
(n-1)d
9
Nhom 2: ns
2
(n-1)d
10
Nhom 3: ns
2
(n-1)d
1
Nhom 4: ns
2
(n-1)d
2
Nhom 5: ns
2
(n-1)d
3
Nhom 6: ns
2
(n-1)d
4
Nhom 7: ns
2
(n-1)d
5
Nhom 8: ns
2
(n-1)d
6,7,8
Nhom 1: ns
1
(n-1)d
10
Nhom 2: ns
2
(n-1)d
10
Nhom 3: ns
2
(n-1)d
1
Nhom 4: ns
2
(n-1)d
2
Nhom 5: ns
2
(n-1)d
3
Nhom 6: ns
2
(n-1)d
4
Nhom 7: ns
2
(n-1)d
5
Nhom 8: ns
2
(n-1)d
6,7,8
Hay
47
48