! "#$%&'$&%! (")"%!* +&" ,-$&./0,# ") *! *"''/1) !)$"%/,% 2!%! "* "#3
2"'$%, 4"* 5$,0, 4" 6 ',)',%4!-! -/") ',) *,# 4!$,# "72"%/0")$!*"# +&" #"
8!-9!) ,-#"%.!4, ") "* 2%/0"% '&!%$, 4"* #/(*, :: ; </) "0-!%(,= ! 0"4/4!
+&" 0">,%!%,) *,# /)#$%&0")$,# ? $@')/'!# "72"%/0")$!*"# #" ,-#"%.!%,) 4"3
$!**"# +&" ), 2,49!) "72*/'!%#" ',) *! $",%9! 4"#!%%,**!4!= ! "#! "#$%&'$&%!
05# 4"$!**!4! #" *" 4"),0/)1 "#$%&'$&%! A)! 4"* 5$,0, 4" 6 ; B) "#$! *"''/1)
#" 2%"$")4" >&#$/A'!% $"1%/'!0")$" *! "#$%&'$&%! A)! /)$%,4&'/")4, 2"%$&%-!3
'/,)"# #,-%" *! "#$%&'$&%! ,-$")/4! ") *! *"''/1) !)$"%/,%; C)$"# 4" "02"D!%
',) *,# $@%0/),# +&" "72*/'!) *! "#$%&'$&%! A)! /)$%,4&'/%"0,# *! $",%9! 4"
2"%$&%-!'/,)"# /)4"2")4/")$"# 4"* $/"02, +&" "# "* /)(%"4/")$" E&)4!0")$!*
") $,4, *, +&" #/(&";
F GH IJH I K ILHIM IK IIIM IN
IO K 
B) 0&'8!# #/$&!'/,)"#= ',0, *! +&" "#$!0,# "#$&4/!)4,= *! "#$%&'$&%!
-5#/'! 4"* 2%,-*"0! *! "72*/'! &) 8!0/*$,)/!), 4!4,= '&?,# !&$,.!*,%"# ?
!&$,."'$,%"# #" #!-") ,-$")"% "7!'$!0")$"; </) "0-!%(,= &)! /)#2"''/1) 05#
A)! ),# 0&"#$%! +&" 8!? 4"$!**"# +&" ), #" 2&"4") "72*/'!% ',) "#" 8!0/*3
$,)/!), #/), +&" #" 4"-" -&#'!% ,$%, 8!0/*$,)/!), 05# (")"%!* +&" ")(*,-"
!* 2%/0"%, ") '/"%$,# *90/$"#; ! $",%9! +&" ),# 2"%0/$" !.!)D!% ") *! ,-3
$")'/1) 4" #,*&'/,)"# !2%,7/0!4!# !* 2%,-*"0! ',02*"$, "# *! 4"),0/)!4!
$",%9! 4" 2"%$&%-!'/,)"#; ! $",%9! 4" 2"%$&%-!'/,)"# $/")" &)! ."%#/1) 2!%!
2"%$&%-!'/,)"# /)4"2")4/")$"# 4"* $/"02,= +&" #" 4/#'&$/%5 ") "#$" '!29$&*,=
? ,$%! ."%#/1)= 2!%! 2"%$&%-!'/,)"# 4"2")4/")$"# 4"* $/"02,= +&" #" ."%5 ")
*! P*$/0! *"''/1) 4" "#$" '&%#,;
Q")$%, 4" *! $",%9! 4" 2"%$&%-!'/,)"# /)4"2")4/")$"# 4"* $/"02, 8!? ! #&
."D 4,# ."%#/,)"#R 2!%! "#$!4,# ), 4"(")"%!4,# ? 2!%! "#$!4,# 4"(")"%!4,#;
B) "#$" '!29$&*, ),# /)$"%"#! *! 4" "#$!4,# 4"(")"%!4,#= ?! +&" *! 0!?,%9! 4"
*,# "#$!4,# +&" 8"0,# '!*'&*!4, 2!%! "* 6 #,) 4"(")"%!4,#= 2"%, #" 2%"#")$!%5
2%/0"%, *! $",%9! 4" 2"%$&%-!'/,)"# 2!%! "#$!4,# ), 4"(")"%!4,# 2!%! 0,#$%!%
*!# /4"!# E&)4!0")$!*"# ") "* '!#, 05# #/02*";
STUT VWXYZ[W \[ Z]^]\]_YZ[W
<&2,)(!0,# +&" #!-"0,# %"#,*."% "7!'$!0")$" *! "'&!'/1) 4" <'8%`4/)3
("% /)4"2")4/")$" 4"* $/"02, 2!%! &) 8!0/*$,)/!), H ; B#, +&/"%" 4"'/% +&"
0
#!-"0,# ,-$")"% #&# !&$,.!*,%"# E (0) ? #&# !&$,E&)'/,)"#
(0)

(0) (0)
H0 (0)
n = E n n .



Hn = (H0 + W )n = En n ,

 

En = En(0) + En(1) + 2 En(2) + . . .

2 (2)
(1)
n = (0)
n + n + n + . . .






<&2,)(!0,# +&" *,# !&$,"#$!4,# (0) #,) ), 4"(")"%!4,#;

</ !* #/#$"0! 4"#'%/$, 2,% H *" !n !4/0,# &)! 2"+&"  ! 2"%$&%-!'/1) /)4"3
0
2")4/")$" 4"* $/"02,  '&5*"# #"%5)
*!# !&$,E&)'/,)"# ? !&$,.!*,%"# 4"* )&".,
8!0/*$,)/!), H  ! %"#2&"#$! !2%,7/0!4! *! 4! *! $",%9! 4" 2"%$&%-!'/,)"#;
*!0"0,#
! *! 2"%$&%-!'/1) /)$%,4&'/4!= 4" E,%0! +&" "# &) 2!%53
0"$%, +&" W
"# 2"+&"  , ',02!%!4, ',)  4" E,%0! +&" W  H ; B) "#$!
#/$&!'/1) "#2"%!0,# +&" *,# !&$,.!*,%"# ? !&$,E&)'/,)"# 4" H = H0 + W 4/3
0
A"%!) 4" *,# ,-$")/4,# 2!%! H 2"%, ), 4"0!#/!4,;  &"#$%, 2%,-*"0!
!8,%!
0
"# #,*&'/,)!% *! "'&!'/1) 4" <'8%`4/)("%
? ,-$")"% #&# !&$,.!*,%"# E ? !&$,E&)'/,)"# 4" &) 0,4, !2%,7/0!4,
n
n
$")/")4, ") '&")$! +&" #9 ',),'"0,#
*!# #,*&'/,)"#
4"* 2%,-*"0! #/) 2"%$&%3
-!%
 ? *!# #,*&'/,)"# 4"
  ), 2&"4") "#$!% 0&? *">,# 4" "**!#; ,% "**,=
2%,2,)"0,# +&" 2,4"0,# ,-$")"% *!# #,*&'/,)"# 4"
  ',0, &) 4"#!%%,**,
") #"%/" 4" 2,$")'/!# ") "* 2!%50"$%,
</ ),# +&"4!0,# ") "* ,%4") '"%, ") $")"0,# *!# #,*&'/,)"# ?! ',),'/4!#
2!%! "* 2%,-*"0! #/) 2"%$&%-!%; ,# #&2"%9)4/'"# (1) = (2) "$' ),# 4!) *!#
',%%"''/,)"# ") 2%/0"%= #"(&)4,= "$' ,%4") ") ; </ *! 2"%$&%-!'/1) "# 2"3
+&"  ! #" "#2"%! +&" *!# ',%%"''/,)"# ") 2%/0"% ,%4") ?! ),# 4") &)! -&")!
!2%,7/0!'/1) !* %"#&*$!4, "7!'$,;
 ")"0,# +&" %"#,*."% *! "'&!'/1)
= $")/")4, ") '&")$!

 ?
 

 


2 (2)
(1)
+
.
.
.
+

(H0 + W ) (0)
n
n
n



(1)
2 (2)
= En(0) + En(1) + 2 En(2) + . . . (0)
n + n + n + . . .



',0, "# &) 2!%50"$%, 2,4"0,# 4"#(*,#!% *! "'&!'/1) !)$"%/,% ") 2,$")'/!#
4" R
,%4")  ") R H (0) = E (0) (0)
0

,%4")  ") R H (1) + W (0) = E (0) (1) + E (1) (0)

,%4")  ") R H (2) + W (1) = E (0) (2) + E (1) (1) + E (2) (0)
n

? !#9 #&'"#/.!0")$" 2!%! 1%4")"# #&2"%/,%"#

! "'&!'/1) 2%/0"%!
,%4") '"%, ")  "# )&"#$%! "'&!'/1) 4" 2!%$/4! #/) 2"%3
$&%-!%; "!0,# *!# ',%%"''/,)"#
") 2%/0"% ,%4") 4" $",%9! 4" 2"%$&%-!'/,)"#
2!%! *!# ")"%(9!# ? 2!%! *!# E&)'/,)"# 4" ,)4!R


   


   
 
  



  





   

</ 0&*$/2*/'!0,# *! "'&!'/1) ") ,%4")  ") !)$"%/,% 2,% *! /D+&/"%3

4! 2,% (0) " /)$"(%!0,# ! $,4, "* "#2!'/, $")"0,# h(0) |H |(1) i +
n
n
0 n
(0)
(0)
(0)
(0) (1)
(1)
(0) (0) ;  ")/")4, ") '&")$! +&"
hn |W |n i = En hn |n i+En hn |n i
(0)
(1)
(0)
(0) (1) #" '!)'"*!) 2,% #"% /(&!*"# "* 2%/0"% ? "*
hn |H0 |n i = En hn |n i
P*$/0, $@%0/), 4" *! "'&!'/1) !)$"%/,%= ',) *, +&" +&"4!
$")/")4, $!03
-/@) ") '&")$! +&" h(0) |(0) i = 1 = 2,% ),%0!*/D!'/1) 4" *!# #,*&'/,)"#
4" *! "'&!'/1)
 n n


(0)
En(1) = h(0)
n |W |n i,



(0)
En En(0) + En(1) = En(0) + h(0)
n |W |n i

 

*, +&" ),# 4/'" +&" *! ',%%"''/1) ") 2%/0"% ,%4") ! *!# ")"%(9!# #/) 2"%3
$&%-!% "# "* .!*,% "#2"%!4, 4" *! 2"%$&%-!'/1) ") "* "#$!4, #/) 2"%$&%-!%R
  !" R # !*'&*"0,# *! ',%%"''/1) ") ")"%(9! !* "#$!4, E&)4!0")$!* 4"*
5$,0, 4" 6 4"-/4! ! &)! 2"%$&%-!'/1) '")$%!* 4"* $/2, W = erE = 4,)4"
0
"# *! '!%(! 4"* "*"'$%1) ? E "# *! !02*/$&4 4" &) '!02, "*@'$%/',;
B*
e8!0/*$,)/!),
0
4"* #/#$"0! 2"%$&%-!4, "# !8,%!

H = H0 + W = H0 + erE0

4,)4" ',),'"0,# *,# !&$,.!*,%"# ? !&$,E&)'/,)"# 4" H R E (0) ? (0) (r) ;

n
0
n`m
B* "#$!4, E&)4!0")$!* 4" H "# ), 4"(")"%!4, (0) (r) ',)
")"%(9!
(0)
E1 =
0
100
"

13,6
(0)
100 (r) = p

a30

exp[r/a0 ].

! $",%9! 4" 2"%$&%-!'/,)"# 4! *! ',%%"''/1) ") ")"%(9! !* "#$!4, E&)4!3

0")$!* 4"* 6 ") 2%/0"% ,%4")
(1)
E1

(0)

(0)

sin d
r2 dr 100 (r)(erE0 )100 (r)
0
0
0
Z
1
= eE0 4 3
dr r3 exp[2r/a0 ]
a0 0
3!
3
4eE0
= ea0 E0 .
=
a30
(2/a0 )4
2
&#!4, *! /)$"(%!* 4"A)/4! ") *! ),$! ! 2/" 4" 25(/)! $ .5*/4! 2!%!
=

<" 8!
r
%"!* ? n ")$"%,;
B) *! A(&%!  #" 0&"#$%! "#+&"05$/'!0")$" *! !2%,7/0!'/1) ") 2%/0"%
,%4") 4" *! $",%9! 4" 2"%$&%-!'/,)"# 2!%! "#$!4,# ), 4"(")"%!4,#; !%!
'!4! ")"%(9! #/) 2"%$&%-!% E (0) 8!? &) P)/', "#$!4, #/) 2"%$&%-!% |ni(0) ;
n

R
0

dr r

exp[r] =

n!
n+1

B* ',)>&)$, 4" "#$!4,# |ni(0) #,) &)! -!#" 2!%! "* "#2!'/, 4" 6/*-"%$ 4"*
2%,-*"0!; H ?! "# 4/!(,)!*
") "#! -!#"= 2!%! ")',)$%!% *! #,*&'/1) "7!'$!
0
-!#$! 4/!(,)!*/D!%
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") 2%/0"% ,%4") 4" $",%9! 4" 2"%$&%-!'/,)"# ',)#/#$" ") 4"#2%"'/!% *,#
"*"0")$,# 4" 0!$%/D ), 4/!(,)!*"# 4" W E%")$" ! *,# 4/!(,)!*"#= 2,% *,
+&" *! #,*&'/1) !2%,7/0!4! ") "#$" ,%4") ! '!4! E (0) "# (0) hn|W |ni(0) ;
n

(0)
1

1
(0)
(0)
(0)

(0)

(0)
2

(0)

(0)
3
(0)
3

. . .
. . .

W 1

W 2

W 3

. . .

W 1

W 2

W 3

. . .

W 1

W 2

W 3

. . .

.
.
.

. . .

. . .

. . .

. . .

   





 
 

     
 
 
    




  
  

   


 
 


   



 
 



  



%

   "    

"  

! "'&!'/1) ") ,%4")  ") !)$"%/,% *! 2,4"0,# %""#'%/-/%






(1)
(0)
H0 En(0) (1)
n .
n = W En

C4"05#= *!# E&)'/,)"# (0) ',) n = 0, 1, 2, . . . E,%0!) &)! -!#" 4"* "#2!'/,
n
E&)'/,)!* 4" )&"#$%, 2%,-*"0!;
,% "**,= '&!*+&/"% E&)'/1) 4" "#$" "#2!'/,
#" 2&"4" "#'%/-/% ") $@%0/),# 4" *!# E&)'/,)"# 4" *! -!#"
(1)
n =

p6=n

Cp(n) (0)
p .

,) *, +&" *! "'&!'/1) !)$"%/,% +&"4!






   


   
 
  



  




H0 En(0)

X

p6=n

 &*$/2*/'!)4, "#$! "'&!'/1) 2,% *! /D+&/"%4! 2,%

$,4, "* "#2!'/, ),# +&"4!

4" 4,)4"





(1)
(0)
Cp(n) (0)
n .
p = W En
(0)

" /)$"(%!)4, !


 


(n)
(0)
(0)
= h(0)
Em
En(0) Cm
m |W |n i,
(n)
Cm
=

(0)

(0)

(0)

(0)

hm |W |n i

 

(0)
m ,

 

,% $!)$,= *! ',%%"''/1) ") 2%/0"% ,%4") 4" 2"%$&%-!'/,)"# ! *!# E&)'/,)"#

4" ,)4! #"%5)

(1)
n =

En Em

(0)
X h(0)
m |W |n i
(0)

(0)

En Em

,= *, +&" "# /(&!*= *! E&)'/1) 4" ,)4! ") 2%/0"% $@%0/), 4" *! $",%9! 4"
2"%$&%-!'/,)"# #"%5
m6=n

(0)
(1)
n (0)
n + n = n +

(0)
X h(0)
m |W |n i

m6=n

(0)
En

(0)
Em

 

(0)
m .

! #&0! 4"* #"(&)4, $@%0/), ! *! 4"%"'8! ',%%" #,-%" $,4,# *,# "#$!4,#
4" H 0"),# "* n ;
0
  !" R # !*'&*"0,# *! ',%%"''/1) ! *! E&)'/1) 4" ,)4! 4"* "#$!4, E&)3
4!0")$!* 4"* 5$,0, 4" 6 4"-/4! ! &)! 2"%$&%-!'/1) '")$%!* 4"* $/2,
',0, !)$"#= 4,)4" "# *! '!%(! 4"* "*"'$%1) ? E "# *! !03
W = erE0
0
2*/$&4 4" &) '!02, "*@'$%/',; B*e 8!0/*$,)/!), 4"* #/#$"0! 2"%$&%-!4,
"#
!8,%!
H = H0 + W = H0 + erE0

4,)4" ',),'"0,# *,# !&$,.!*,%"# ? !&$,E&)'/,)"# 4" H R E (0) ? (0) (r) ;

n
0
n`m
B* "#$!4, E&)4!0")$!* 4" H "# ), 4"(")"%!4, (0) (r) ',)
")"%(9!
(0)
E1 =
0
100
"

13,6
(0)
100 (r) = p

a30

exp[r/a0 ].

! $",%9! 4" 2"%$&%-!'/,)"# 4! *! ',%%"''/1) ! *! E&)'/1) 4" ,)4! 4"*

"#$!4, E&)4!0")$!* 4"* 6 ") 2%/0"% ,%4")
(1)
1

q6=1,`,m

= eE0

R 2
X

q6=1,`,m

R
0

sin d

R
0

(0)

(0)

r2 dr q`m (r)(erE0 )100 (r)

(0)

(0)

E1 Eq
R 2
R
R
(0)
(0)
d 0 sin d 0 dr q`m (r)r3 100 (r)
0
(0)

(0)

E1 Eq

(0)

q`m (r)
(0)

q`m (r).

</ %"',%4!0,# +&" (r) = R (r)Y (, ) ? *!# %"*!'/,)"# 4" ,%$,3

n`m
n`
`m
),%0!*/4!4 4" *,# !%01)/',#
"#E@%/',#
(1)
1

= eE0
= eE0

`,0 m,0

q6=1,`,m
R
X
0
q6=1

R
0

dr Rq`
(r)r3 R10 (r)
(0)
E1

dr Rq0
(r)r3 R10 (r)
(0)
(0)
E1 Eq

(0)
Eq

(0)

q`m (r)

(0)

q00 (r)

"R

(r)r3 R10 (r) (0)

dr R20
200 (r)
1 14
#
R

dr R30
(r)r3 R10 (r) (0)
0
+
300 (r) + . . .
1 19

"
#

V
eE0 (

)a0 ( )
81 3 (0)
512 (0)

(r) +
300 (r) + . . . ,
 
=
13,6(eV )
243 200
256

eE0
=
13,6(eV )

4,)4" #" 8!) &#!4, *!# E,%0!# 4" *!# E&)'/,)"# 4" ,)4! %!4/!*"# 2!%! "*
6 4!4!# ") *! *"''/1) !)$"%/,%; <" 8!) "#'%/$, "72*9'/$!0")$" *!# &)/4!4"#
2!%! 0,#$%!% +&" *,# ',"A'/")$"# #,) !4/0")#/,)!*"#= ',0, ',%%"#2,)4";
STST VWXYZ[W Z]^]\]_YZ[W
B) "#$! #&-#"''/1) #" 2%"#")$! *! (")"%!*/D!'/1) 4" *! $",%9! 4" 2"%$&%3
-!'/,)"# 4/#'&$/4! ") *! !)$"%/,% !* '!#, 4" "#$!4,# 4"(")"%!4,#; B#$" "# "*
'!#, +&" ),# /)$"%"#! !8,%! ?! +&" *,# "#$!4,# ,-$")/4,# ") *! *"''/1) !)$"%/,%
2!%! "* 5$,0, 8/4%,("),/4" #,)= ") (")"%!*= 4"(")"%!4,#;
!%$/0,# 4"* 0/#0, 2&)$, +&" ") *! #&-#"''/1) !)$"%/,%= &) #/#$"0! "#$5
4"#'%/$, 2,% &) 8!0/*$,)/!), +&" "#$5 E,%0!4, 2,% &)! 2!%$"
H  '&?,#
!&$,.!*,%"# ? !&$,E&)'/,)"# #!-"0,# ,-$")"% ? ,$%! 2!%$"= +&" "# 02"+&"  !
%"#2"'$, ! H = +&" $%!$!%"0,# ',0, &)! 2"%$&%-!'/1)
0

H = H0 + W,

',)

(0)

(0)

H0 n,i = En(0) n,i

 

 

? E (0) ? (0) ',),'/4,#
i = 1, 2, . . . )&0"%! 4/#$/)$!# E&)'/,)"# !#,'/!4!# !*

n
n,i
0/#0,
!&$,.!*,%
; <&2,)(!0,# +&" "* )/."* 4" /)$"%@# E (0) "# k ."'"# 4"("3

)"%!4,; B#, #/()/A'! +&" 8!? k E&)'/,)"# 4" ,)4! (0) ',)mi = 1, 2, . . . , k +&"
mi
#,) !&$,E&)'/,)"# 4" H !#,'/!4!# !* 0/#0, !&$,.!*,%
E&)'/,3
(0) ; B#!#
Em
k
0
)"# 4" ,)4! E,%0!) &)! -!#" 4"* "#2!'/, k34/0")#/,)!* !#,'/!4,
!* !&$,.!*,%
(0) = *, +&" +&/"%" 4"'/% +&" '&!*+&/"% ',0-/)!'/1) */)"!* 4" "**!# $!0-/@)
Em
"# !&$,E&)'/1) 4" H !#,'/!4! !* 0/#0, !&$,.!*,% E (0) ;  &#'!0,# !8,%!
0
#,*&'/,)"# !2%,7/0!4!#
?  4" *! "'&!'/1) 4"m<'8%`4/)("%

E
m


   


   
 
  



  




  

Hm = (H0 + W )m = Em m .

</(&/")4, "* 0/#0, 2%,'"4/0/")$, 4" *! #&-#"''/1) !)$"%/,%= 4"#!%%,**!0,#

*!# #,*&'/,)"# ") #"%/" 4" 2,$")'/!# ") "* 2!%50"$%,


 

(2)
(1)
(0)
+ ...
+ 2 Em
+ Em
Em = Em
(1)
m = (0)
m + m + . . . =

(H0 + W )



") *! "'&!'/1)


(0)
Ci mi

  

+ (1)
m + . . .

i=1

(0)
Em

(1)
Em

+ ...

 

(0)

Ci mi + (1)
m + . . .

i=1

?= 4" )&".,= #&#$/$&?")4,

k
X

k
X

k
 X

,-$")"0,#

!
(0)
Ci mi

(1)
m

+ ...

+&" 2,4"0,# #"2!%!% ") *,# 4/#$/)$,# 1%4")"# ") /(&!* +&" !)$"#
,%4")  ") R H Pk C (0) = E (0) Pk C (0) ;
i=1

i=1

,%4")  ") R H (1) +W Pk

0

mi

i=1

(0)

i=1

(0)



 

mi

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8!'"% &#, 4" *! $",%9! 4" 2"%$&%-!'/,)"# 2!%! "#$!4,# ), 4"(")"%!4,# ',0,
>&#$/A'! "* $",%"0! +&" 4"0,#$%!0,# !)$"#; ,% "**,= *!# ',%%"''/,)"# ! *!#
")"%(9!# E (0) 4"-/4!# ! *! /)$"%!''/1) "#29)31%-/$! ") 2%/0"% ,%4") 4" $",%9!
n
4" 2"%$&%-!'/,)"#
#"%5
(1)(so)

En`
#

= hn`s; jm|Wso |n`s; jmi =


,0, *,# "#$!4,# |n`s; jmi #,) !&$,"#$!4,# 4" j 2 = `2 ? s2 2,4"0,# ".!*&!%
(1)(so)

En`

= hn`|(r)|n`i

[j(j + 1) `(` + 1) s(s + 1)] ~2

.
2





!%! $")"% &)! "72%"#/1) "72*9'/$! 4" *! ',%%"''/1) #1*, 8!? +&" '!*'&*!%
hn`|(r)|n`i =

1
hn`s; jm|(r) j 2 `2 s2 |n`s; jmi.
2

"'"#/$!0,# hn`| 1 |n`i +&" "#

1
Ze2
hn`| 3 |n`i.
22 c2
r



r3

hn`|

1
Z3
|n`i
=
.
r3
a30 n3 `(` + 1/2)(` + 1)



# ,) "#$,= ? $")/")4, ") '&")$! +&"

?! +&" "# "* "#29) 4"* "*"'$%1))
s = 1/2
2,4"0,# "#'%/-/% *! ',%%"''/1) "#29)31%-/$!


   


   
 
  



  



(1)(so)

En`

Z3
Ze2
[j(j + 1) `(` + 1) 3/4] ~2
,
3
2
2
3
2 c a0 n `(` + 1/2)(` + 1)
2

 
"72%"#/1) +&" .!*" #/"02%" +&" ` 6= 0 = ?! +&" #/ ` = 0 ), 8!? ',%%"''/1) "#29)3
1%-/$!; B#$! P*$/0! "72%"#/1) *! 2,4"0,# "72*/'/$!% !P) 05# #/ %"',%4!0,#
+&" 4"-/4, ! +&" s = 1/2 *,# .!*,%"# +&" 2&"4" $,0!% j #"%5) ` + 1/2 ?
= ',) *, +&"
` 1/2
(1)(so)
En`

Z 4 e4

=
4c2 a20 n3 `(` + 1/2)(` + 1)
2

`
si j = ` + 1/2
(` + 1) si j = ` 1/2

B#$! "'&!'/1) 0&"#$%! +&" #" E!.,%"'") ")"%(@$/'!0")$" *,# "#$!4,# ',)
j =
',) %"#2"'$, ! *,# j = ` + 1/2 2"%, "# /02,%$!)$" ),$!% +&"
` 1/2
(1)(so)

En`

(1)(so)

E
(para j = ` + 1/2)
= n`
`

(para j = ` 1/2)
(` + 1)



, *, +&" "# /(&!*= A>!4! &)! ` *! /)$"%!''/1) "#29)31%-/$! #"2!%! "#" "#$!4,
") 2j + 1 = 2(` + 1/2) + 1 = 2` + 2 "#$!4,#
4"(")"%!4,#  0"),# */(!4,#
+&" "* ,%/(/)!* ") &)! '!)$/4!4 A = B/((` + 1/2)(` + 1)) ? ") 2j + 1 =
"#$!4,# 4"(")"%!4,#  05# */(!4,# +&" "* ,%/(/)!* ") &)!
2(` 1/2) + 1 = 2`
'!)$/4!4 B 0 = A/(`(` + 1/2))
4" E,%0! +&"
"* '")$%,/4" 4" *! ")"%(9! #&0!
4" $,4,# *,# 4"#2*!D!0/")$,# 2%,4&'/4,# ',) %"#2"'$, !* "#$!4, ,%/(/)!*
 ),
.!%9! 4"-/4, ! *! /)$"%!''/1) "#29)31%-/$!
2(` + 1)

A
A
= 2`
(` + 1/2)(` + 1)
`(` + 1/2)



',0, #" 0&"#$%! ") *! A(&%! 2!%! "* '!#, 4" ` = 1 ;

Acoplamiento espinorbita

n, l=1

A
2A

H0

j=l+1/2=3/2

4 estados

j=l1/2=1/2

2 estados

H + Wso
0

  



     
   


 
  
  

n, ` = 1
%


     
 



 
     


 
 


j

` 1/2
` + 1/2 %
  
  
 



  
 



 





  
%


T
T

V  X _   \[ Z]
Y_   \
C4"05# 4" *!# 4,# ',%%"''/,)"# ?! 0")'/,)!4!#= ") "* $%!$!0/")$, %"*!3
$/./#$! !2!%"'" &) $@%0/), !4/'/,)!* +&" !'$P! #1*!0")$" '&!)4, ` = 0 ? #"
4"),0/)! $@%0/), 4" Q!% /)
WDarwin =

~2
Ze2 (r).
22 c2

B#$" $@%0/), 4/'" +&" "* "*"'$%1) ), 2&"4" "#$!% ") r = 0 = "# 4"'/%= ), 2&"4"
"#$!% 4")$%, 4"* 2%,$1);
! ./0,# +&" #1*!0")$" 8!?
&)! 2%,-!-/*/4!4 ),
)&*! 4" +&" "* "*"'$%1) "#$@ 4")$%, 4"* )P'*", 2!%! *,# "#$!4,# s
` = 0 ;
!%! $")"% ") '&")$! "#$" $@%0/), &$/*/D!0,# *! $",%9! 4" 2"%$&%-!'/,)"# ?=
!* /(&!* +&" ") *,# '!#,# !)$"%/,%"#= &#!0,# *! -!#" |n`s; jmi ;
! +&" ,2"%!4,%
',)0&$! ',)
2,4"0,# &#!% *! $",%9! 4" 2"%$&%-!'/,)"# 2!%! "#$!4,#
j2
), 4"(")"%!4,# (r)
(1)(D)

En`

= hn`s; jm|WD |n`s; jmi =



"* "#$!4, |n 0 1/2; 1/2 mi = |n ` = 0 m =

`
"* ,2"%!4,% 4"*$! ), !'$P! #,-%" *!# .!%/!-*"#
4" "#29) ? *! E&)'/1) 4" ,)4! 4" "#29) "#$5 ),%0!*/D!4! ),# +&"4!

"%, 2!%!

4Ze2 ~2
hn`s; jm|(r)|n`s; jmi.
82 c2

` = 0 s = 1/2
; # ,0,
0i |s = 1/2 ms = mi
(1)(D)

En`

= hn ` = 0 s = 1/2; j = 1/2 m|WD |n ` = 0 s = 1/2; j = 1/2 mi

= hs = 1/2 m|s = 1/2 mihn ` = 0 m` = 0|WD |n ` = 0 m` = 0i
4Ze2 ~2

hn00|(r)|n00i,
=


2
2
8 c

2,% *! 4"A)/'/1) 4" *! "#$" P*$/0, "*"0")$, 4" 0!$%/D ), "# 05# +&" "*
'&!4%!4, 4" *! E&)'/1) 4" ,)4! ',) )P0"%,# '&5)$/',# n, ` = 0, m = 0
".!*&!4! ") "* ,%/(")
(1)(D)

En`

4Ze2 ~2
2
|n00 (0)| .
82 c2

!%! *!# E&)'/,)"# s = +&" #,) *!# P)/'!# +&" ), #" !)&*!) ") r = 0 = #!-"0,#
+&"

|n`=0m=0 (0)| =

Z3
.
n3 a30

,% *, +&" *! ',%%"''/1) +&" 4! "* $@%0/), 4" Q!% /) "#

(1)(D)

En`

= 2

Z 4 e4
2c2 n3 a20

solo si

`=0



+&" #1*, !E"'$! ! *,# "#$!4,# ',) ` = 0 ? *"# !&0")$! */("%!0")$" *! ")"%(9!;


   


   
 
  



  




T

T  Y ]WX_
 X
_Y  \Y Z]  
C&+&" 8"0,# $%!$!4, *!# $%"# ',%%"''/,)"# 0")'/,)!4!# 2,% #"2!%!4,= ")
*! %"!*/4!4 *!# $%"# !'$P!) ',)>&)$!0")$" ") "* 5$,0, 4" 6 ; ,% "**,= "* "E"'$,
+&" ,-#"%.!%"0,# "72"%/0")$!*0")$" #"%5 *! #&0! 4" *,# $%"#; C "#$! #&0! #"
*" 4"),0/)! &#&!*0")$" ',%%"''/1) 4" "#$%&'$&%! A)! 4"* 5$,0, 4" 8/4%1("),
Wef = Wrel + Wso + WD ,



? *! ',%%"''/1) ") ")"%(9! +&" #" 2%,4&'" #,-%" *! ")"%(9! '!*'&*!4! ") *!
*"''/1) !)$"%/,% #"%9!
(1)
Enj (ef )



Z 4 e4
1
3
=
.

2c2 n3 a20 4n j + 1/2

2



C ."'"# #" #&"*") &#!% *!# 4"A)/'/,)"# 4" *! ',)#$!)$" 4" "#$%&'$&%! A)! +&"
"# &)! ',)#$!)$" #/) 4/0")#/,)"#=
1
e2
=
,
~c
137

? 4" *! ")"%(9! 4"* "#$!4, E&)4!0")$!* 4"* 5$,0, 4" 8/4%1("),

(0)

E1

e2
= 13,6 eV,
2a0





4,)4" #" 8! &#!4, *! 4"A)/'/1) 4"* %!4/, 4"  ,8%R

a0 =

1 ~2
.
me2



 

,) "**,= *! ',%%"''/1) 4" "#$%&'$&%! A)! #" "#'%/-"

(1)

Enj (ef ) =

Z4
(0)
|E1 | 2
n3


1
3

< 0,
4n j + 1/2

 

',) *, +&" *! ")"%(9! 4" *,# )/."*"# 4"* 5$,0, 4" 6 $")/")4, ") '&")$! *!
"#$%&'$&%! A)! 4"2")4" 4" n ? j ? "#
(1)

Enj (ef ) = En(0) + Enj (ef ) =

Z2
Z4 2
(0)
|E
|

1
n2
n3

1
3

j + 1/2 4n

(0)

|E1 |.

  
C*(&)!# ."'"# ! |E (0) | #" *! $,0! ',0, &)/4!4 4" ")"%(9! ? #" *! 4"),0/)!
1
 ?4-"%(R  ?4-"%(
 ? 
; " ;

B* "E"'$, (*,-!* 4" *! ',%%"''/1)
4" "#$%&'$&%! A)! "# +&" *,# )/."*"# "#$5)
*/("%!0")$" 05# */(!4,# +&" *,# 4" H '!*'&*!4,# ") *! *"''/1) !)$"%/,%; !
0
',%%"''/1)R
#" 8!'" 0"),% !* !&0")$!% n , j =

'%"'" 0&'8, !* !&0")$!% Z ?! +&" .! ',0, Z 4 =

2!%! "* 6 = "* "#$!4, E&)4!0")$!*
"#$5 05# */(!4, +&" "* 4" ") &)!
0
'!)$/4!4 1,81 104 " ; "0,# +&" "E"'$/.!0")$" "# 0&'8, H0"),%
+&"
*! #"2!%!'/1) ")$%" )/."*"# ")"%(@$/',# 4" H =
0
2!%! &) .!*,% 4!4, 4" n = *! #"2!%!'/1) ")$%"
"* "#$!4, 05# */(!4,
` =
?
"*
0"),#
*/(!4,
"#

` = n 1, j = ` + 1/2 = n 1/2 
0, j = 1/2 
En =

Z2 2

n3

1
n

(0)

|E1 |

+&" #" 8!'" 0"),% !* !&0")$!% n ;

 "!0,# &) ">"02*, #/02*" 2!%! /*&#$%!% *, +&" 8"0,# "72*/'!4,; B* $%!3
$!0/")$, 05# #/02*" 4"* 6 4! +&" *! ")"%(9! #1*, 4"2")4" 4" n ; ,% $!)$,=
") "#$! !2%,7/0!'/1)= "* )/."*
"#  ."'"# 4"(")"%!4, ?! +&" ',) /(&!*
")"%(9! 8!? "#$!4,# ',) ` = 0n =
 2"#$!4,  ? 

"#$!4,#= m = 1, 0 *,
`
+&" 4! &) $,$!* 4"  "#$!4,#; </ ',)#/4"%!0,# *!# 4,# ',02,)")$"#
4" "#29)
4!)  ; </) "0-!%(,= #" ,-#"%.! "72"%/0")$!*0")$" +&" 2!%! n = 2 8!? 
"#$!4,# 0&? 2%17/0,# ") ")"%(9! 2"%, ), 4"(")"%!4,#; ! #"2!%!'/1) ,-#"%3
.!4! "72"%/0")$!*0")$" "#  ;
 cm1
."% ),$! ! 2/" 4" 25(/)! #,-%" "#$!#
&)/4!4"#  ;
 "!0,# *, +&" ),# 4! *! "#$%&'$&%! A)! ."% A(&%!  ; <"(P) *, ./#$,


!%%/-!= *! #"2!%!'/1) ")$%" *,# "#$!4,# 4" "#$%&'$&%!
A)! n = 2, ` = 1, j = 3/2
? n = 2, ` = 1, j = 1/2 ") "* 6

  "#
E2,1

1
= 3
2

1
137

2 

1
1
2

= 4,53 105 (eV )

13,6(eV ) = 4,53 105 (eV )

1(cm1 )
= 0,365 cm1 .
1,2378 104 (eV )

 


 

") 2"%E"'$, !'&"%4, ',) *, ,-#"%.!4, "72"%/0")$!*0")$";

T T

[XY  \ ]W  ]  X_[W    Y

!%! /4")$/A'!% &) "#$!4, 4"* 5$,0, 4" 6 #" #&"*" &#!% *! ),$!'/1)

n2s+1 `j
 



 
 
   
  
   


   
cm1



 





E = h =




1(cm)
hc
= 1,2378 104 (eV )

(cm)

1 cm1 = 1,2378 104 eV %


   


   
 
  



  



Estructura fina
n=2, (l=1,l=0)
. . .

. . .

E n,l

n=2, l=1, j=3/2

n=2, l=1, j=1/2 y n=2, l=0, j=1/2

n=1, (l=0)
n=1, l=0, j=1/2
H0
H + Wrel + Wso + W
0

Darwin



 


 



  
 



n=1 n=2

 
  
  
  
 




 


     
 





  
 %   


   



 

j%
%

 

4,)4" n "# "* )P0"%, '&5)$/', 2%/)'/2!*= s "# "* "#29)
") "#$" '!#, s = 1/2 =
"# "* 0,0")$, !)(&*!% ,%-/$!* ? "# "* 0,0")$, !)(&*!% $,$!* 4"* "*"'3
`
$%1); C4"05#= 2,% %!D,)"# 8/#$1%/'!#j#" &#!) *"$%!# 2!%! 4"#/()!% "* 0,0")$,
!)(&*!% ,%-/$!* #/(&/")4, *! "+&/.!*")'/!
`=

0
s

1 2 3
p d f

...
...

C#9= "* "#$!4, E&)4!0")$!* 4"* 6 #"%5 R 12 s ; ,# "#$!4,# +&" #" ,-$/")")
1/22&"# $/")") /(&!*"#
2!%! n = 2 #"%5)R 22 s = 22 p
4"(")"%!4,#
? ?
n j
1/2
1/2
;
2
2 p
3/2


K  I 
TUT  ]W[  ]_  Y ] 
Y  \ Z]    _  Z  \^]_ ]\  [_  Y  YX_  Y 
B) "#$" !2@)4/'" #" 0&"#$%! +&" %"#,*."% *! "'&!'/1) 4" <'8%`4/)("% "#
"+&/.!*")$" ! 4/!(,)!*/D!% "* 8!0/*$,)/!), ") &)! -!#";
C)$"# 4" !-,%4!% "#" 2%,-*"0!= .!0,# ! ',)#/4"%!% &) 2%,-*"0! 05#
#")'/**,= 4"#4" &) 2&)$, 4" ./#$! 2&%!0")$" 0!$"05$/',; <&2,)(!0,# +&"
$")"0,# ,2"%!4,% A = 4"A)/4, ") &) '/"%$, "#2!'/, ."'$,%/!* 4" 4/0")#/1)  =
? +&"%"0,# %"#,*."% "* 2%,-*"0! 4" !&$,.!*,%"#R
Au = u,

 

Ai = ai + bj,

 

Aj = ci + dj.

 

u = u1 i + u2 j.



 

"# 4"'/%= +&"%"0,# ")',)$%!% *,# ."'$,%"# 2%,2/,# 4" A = u $!*"# +&" *! 0!$%/D
= !'$&!)4, #,-%" 4/'8,# ."'$,%"#= ),# 4".&"*." "* 0/#0, ."'$,% 0&*$/2*/'!4,
A
2,% &)! ',)#$!)$"
 ; </ 2!%$/0,# 4" &)! -!#" 4" "#$" "#2!'/, ."'$,%/!* 4"
4/0")#/1) = ! *! +&" 4"),$!0,# 2,% i = j = "* ,2"%!4,% A +&"4!%5 ',03
2*"$!0")$" 4"$"%0/)!4, #/ ',),'"0,# '10,
!'$P! 4/'8, ,2"%!4,% #,-%" *,#
."'$,%"# 4" *! -!#"; B) (")"%!*= *! !''/1) 4" A #,-%" *,# "#$!4,# i ? j 4".,*."%5
&)! ',0-/)!'/1) */)"!* 4" 4/'8,# "#$!4,#R


C#/0/#0,= *,# "#$!4,# u #"%5) &)! '/"%$! ',0-/)!'/1) */)"!* 4" *,# "#$!4,#
4" *! -!#"R
# !*'&*!% *,# !&$,."'$,%"# "# 2&"# "+&/.!*")$" ! ,-$")"% *,# ',"A'/")$"#
u
u1
? u ") &)! -!#" 4"$"%0/)!4!;
2
 #!)4, "#$!# 4,# P*$/0!# "'&!'/,)"#= 2,4"0,# "#'%/-/% *! "'&!'/1) 4"
!&$,.!*,%"#
  ") *! E,%0! 0!$%/'/!*R

ab
cd



u1
u2

u1
u2

,% $!)$,= %"#,*."% "* 2%,-*"0! 4" !&$,.!*,%"#

"# "+&/.!*")$" ! 4/!3

 
(,)!*/D!% *! #/(&/")$" 0!$%/DR

ab
cd

!#"0,# !8,%! !* 2%,-*"0! '&5)$/', +&" ),# /)$"%"#!;

&"%"0,# %"#,*."%
*! "'&!'/1) 4" <'8%`4/)("% /)4"2")4/")$" 4"* $/"02, 4!4! 2,%R

Hk = Ek k ,

 

+&" ), "# 05# +&" &)! "'&!'/1) 4" !&$,.!*,%"# 2!%! "* ,2"%!4,% 8!0/*$,)/!),;
B* 2%,-*"0! ',)#/#$" ") ")',)$%!% *!# !&$,E&)'/,)"# ? #&# ',%%"#2,)4/")$"#
k
!&$,.!*,%"# E 2!%! k = 1, 2, . . .
k


   


   
 
  



  




6!'/")4, &) 2!%!*"*/#0, ',) "* 2%,-*"0! 0!$"05$/', %"#&"*$, !* 2%/)'/2/,

4" "#$! #"''/1)= 2!%$/0,# 4" &)! -!#" 4"* "#2!'/, 4" 6/*-"%$ 4"* 2%,-*"0!= ! *!
+&" 4"),$!0,# 2,% }, con n = 1, 2, . . . ; ,# !&$,"#$!4,# +&" +&"%"0,#
n
k
'!*'&*!%= #" 2,4%5) {
4"#!%%,**!%
") *! -!#" { } R
n

k =

c(k)
n n .



n=1

<&#$/$&?")4, "#$" 4"#!%%,**, ") *! "'&!'/1) 4" <'8%`4/)("%

 R

H

c(k)
n n = Ek

n=1

c(k)
n n .





n=1

Q"$"%0/)!% *,# !&$,"#$!4,# } "# 2&"# "+&/.!*")$" ! 4"$"%0/)!% *,# ',"A3

'/")$"# 4"* 4"#!%%,**,= {c(k) }{
; k&*$/2*/'!)4, ! *! /D+&/"%4! "#$! "'&!'/1) 2,%
n
" /)$"(%!)4, ") $,4, "* "#2!'/,R

n=1

c(k)
n hm|H|ni = Ek

n=1

4,)4" 8"0,# &#!4, *! ),$!'/1) 4" Q/%!'R

(k)
c(k)
n hm|ni = Ek cm ,





n |ni,
dV m n hm|ni,
dV m Hn hm|H|ni.

1$"#" +&" ") "* P*$/0, 2!#, 4" *! "'&!'/1)
   8"0,# &$/*/D!4, *!# 2%,2/"3
4!4"# 4" ,%$,(,)!*/4!4 4" *,# "#$!4,# 4" *! -!#"=
;
hm|ni = m,n
! "72%"#/1)
   #" 2&"4" "#'%/-/% 4" 0!)"%! 05#
$%!)#2!%")$" ") E,%0!
0!$%/'/!*R


(k)
(k)
c1
c1
H1,1 H1,2 H1,3 . . .
(k)
(k)
H2,1 H2,2 H2,3 . . .
c2

c2

= Ek
(k)
H3,1 H3,2 H3,3 . . .

c(k)
c
;; ;; ; ; ;
;;
3
3
;
;

;
;
; ; ;

;
;
4,)4" 8"0,# "02*"!4, *! ),$!'/1) #/02*/A'!4! H hn|H|mi ; "0,# 2,%
nm
$!)$, +&" %"#,*."% *! "'&!'/1) 4" <'8%`4/)("% /)4"2")4/")$"
4"* $/"02, "#
"+&/.!*")$" %"#,*."% &)! "'&!'/1) 0!$%/'/!* */)"!*; !%! ,-$")"% *,# !&$,.!*,3
%"# ? !&$,."'$,%"# $")4%"0,# 2&"# +&" 4/!(,)!*/D!% *! 0!$%/DR

H1,1 H1,2 H1,3 . . .

H2,1 H2,2 H2,3 . . .

H3,1 H3,2 H3,3 . . . .

;; ;; ; ;
;;

;
; ; ;
 1$"#" +&" "#$! 0!$%/D #" 2&"4" /)$"%2%"$!% ',0, &)! %"2%"#")$!'/1) 4"*
,2"%!4,% 8!0/*$,)/!), ") *! -!#" { } ;
n

K  I



TUT
 X]\  \ Z]  Y ]   _]W  \ Z]  Y  [   Y   ]\X[ ]W  \   _  XY

B* 2,$")$/!* 4" "#29) 1%-/$! !2!%"'" 4" 0!)"%! )!$&%!* ") &) $%!$!0/")$,
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