CHEM 342. Spring 2002. Problem Set #4. Answers.

Spin Wave Functions

1. Which o the ollowing spin w!"e #nctions !re s$mmetric with respect to the
e%ch!nge o electrons&
( ) ( )
( ) ( )
( ) ( ) ( ) ( ) [ ]
( ) ( ) ( ) ( ) [ ] 2 1 2 1
2
2
2 1 2 1
2
2
2 1
2 1
4
3
2
1

+


'he res#lts o the perm#t!tor oper!tor on the !bo"e w!"e #nctions !re !s ollows
( ) ( ) [ ] ( ) ( )
( ) ( ) [ ] ( ) ( )
( ) ( ) ( ) ( ) [ ] ( ) ( ) ( ) ( )
( ) ( ) ( ) ( ) [ ] ( ) ( ) ( ) ( )
4 4
3 3
2 2
1 1
1 2 1 2 2 1 2 1
( (
1 2 1 2 2 1 2 1
( (
1 2 2 1
( (
1 2 2 1
( (

+ +


P P
P P
P P
P P
'he w!"e #nctions 3 2 1
) )
!re s$mmetric bec!#se the eigen"!l#e o the perm#t!tor
oper!tor is *1. 'he w!"e #nction
4
is !ntis$mmetric bec!#se the eigen"!l#e o the perm#t!tor
oper!tor is 1 .
2. Show th!t the ollowing spin #nction
( ) ( ) ( ) ( ) [ ] 2 1 2 1
2
2
+
is !n eigen#nction o the tot!l z component o spin !ng#l!r moment#m or ! two+electron
s$stem. Wh!t is the eigen"!l#e&
,or ! two+electron s$stem) the tot!l - component is gi"en b$
( ) ( ) 2
(
1
( (
z z z
S S S +
where the spin oper!tors !n. w!"e #nctions !re rel!te. b$
( ) ( ) ( )
( ) ( ) ( ) i i i S
i i i S
z
z


2
(
2
(

'hereore
1
CHEM 342. Spring 2002. Problem Set #4. Answers.
( ) ( ) [ ] ( ) ( ) ( ) ( ) [ ]
( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) [ ]
( ) ( ) ( ) ( ) ( ) ( ) ( ) ( )
( ) ( ) ( ) ( )
( ) ( ) ( ) ( ) [ ]
,
_

,
_

+
1
]
1

,
_

+
,
_

1
]
1

+
,
_

+
,
_

+
+ + +
1
]
1

+ +
2 2 2 2
2 1 2 1
2
2
(
2 2
2 1
2 2
2 1
2
2
(
2
2
1 1
2
2 2
2
1 1
2
2
2
2
(
2 2
(
1 1 1
(
2 2 2
(
1 1 1
(
2
2
2
(
2 1 2 1
2
2
2
(
1
( (
3 3
3
3
3
3



z
z
z
z z z z z
z z z
S
S
S
S S S S S
S S S
3

is !n eigen#nction o
z
S
(
with !n eigen"!l#e o 0
2 2


Slater Determinant
3. /se the Sl!ter .etermin!nt to !rri"e !t ! w!"e #nction to .escribe the gro#n. st!te o !
two+electron s$stem s#ch !s He. E%press the res#lting w!"e #nction in terms o the 1s sp!ti!l
w!"e #nction or e!ch electron 0
( ) 1
1s

!n.
( ) 2
1s

1) !n. o the spin w!"e #nctions or e!ch

electron ( ) ( ) ( ) ( ) [ ] 2 !n. ) 1 ) 2 ) 1 .
( ) ( ) ( ) ( )
( ) ( ) ( ) ( )
( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) [ ] 2 2 1 1 2 2 1 1
2
1
2 2 1 1
2 2 1 1
2 2
1
1 1 1 1
1 1
1 1




s s s s
s s
s s
Angular Momentum; Russell-Saunders coupling vs. jj-coupling; Term Symbols
4. C!lc#l!te the !llowe. "!l#es o j or ! d electron.
s l s l s l j + + )....) 1 )
,or ! d electron) l 3 2) s 3 142. 'hereore)
2
3
)
2
5
j
5. 'he 6#!nt#m n#mber 7 represents the tot!l orbit!l !ng#l!r moment#m) !n. .escribes
l-l coupling o the orbit!l !ng#l!r moment#m o two or more electrons. 8etermine the "!l#es o
7 or two d electrons. Wh!t !re the correspon.ing letter s$mbols& Hint9 'he 6#!nt#m n#mber 7
m!$ h!"e "!l#es between the s#m o the l "!l#es o the in.i"i.#!l electrons !n. the !bsol#te
"!l#e o the .ierence o these n#mbers. 2 1 2 1 2 1
)...) 1 ) l l l l l l L + +
'he "!l#e o l or d electrons is 2. 'hereore)
0 ) 1 ) 2 ) 3 ) 4
2 2 ) 3 2 2 ) 2 2 2 ) 1 2 2 ) 2 2

+ + + +
L
L
'he "!l#e o 7 .etermines the letter s$mbol !s ollows) 7 3 0 or S: 7 3 1 or P: 7 3 2 or
8: 7 3 3 or ,: 7 3 4 or ;: etc.
'hereore) the letter s$mbols correspon.ing to 7 3 4) 3) 2) 1) 0 !re ;) ,) 8) P) !n. S
respecti"el$.
2
CHEM 342. Spring 2002. Problem Set #4. Answers.
<. 'he 6#!nt#m n#mber S represents the tot!l spin !ng#l!r moment#m) !n. .escribes the
s-s coupling o the spin !ng#l!r moment#m o two or more electrons. 8etermine the "!l#es o S
or two d electrons.
,or two electrons
2
1
2
1
)
2
1
2
1
+ S
0 ) 1 S
=. 'he 6#!nt#m n#mber J represents the tot!l !ng#l!r moment#m) !n. .escribes the
>#ssel+S!#n.ers co#pling between L !n. S. 8etermine the "!l#es o J or two d electrons. Hint:
the !llowe. "!l#es o J !re gi"en b$
S L S L S L J + + )...) 1 )

7 3 4) S 3 0) ? 3 4
7 3 4) S 3 1) ? 3 5) 4) 3
7 3 3) S 3 0) ? 3 3
7 3 3) S 3 1) ? 3 4) 3) 2
7 3 2) S 3 0) ? 3 2
7 3 2) S 3 1) ? 3 3) 2) 1
7 3 1) S 3 0) ? 3 1
7 3 1) S 3 1) ? 3 2) 1) 0
7 3 0) S 3 0) ? 3 0
7 3 0) S 3 1) ? 3 0) 1
@. Write the complete term s$mbols or the ollowing st!tes
A!B 7 3 4) S 3 1) ? 3 5:
AbB 7 3 2) S 3 0) ? 3 2:
AcB 7 3 0) S 3 0) ? 3 0
'he orm!t or the term s$mbols is
J
S
X
1 2 +
. 'he "!l#e o 7 .etermines the letter s$mbol
!s ollows) 7 3 0 or S: 7 3 1 or P: 7 3 2 or 8: 7 3 3 or ,: 7 3 4 or ;: etc. 'his le!.s to the
ollowing term s$mbols9
A!B
3
;5
AbB
1
82
AcB
1
S0
C. 8etermine the electronic conig#r!tion or !n !tom with the term s$mbol
4
S342.
'he "!l#e o the 6#!nt#m n#mber S c!n be .etermine. rom the m#ltiplicit$.
S
M S
S

+
2
3
4 1 2
3
CHEM 342. Spring 2002. Problem Set #4. Answers.
'his implies th!t there !re three #np!ire. electrons. 'he S letter s$mbol gi"es
0
L
M L . 'his in.ic!tes th!t there is one electron in e!ch o the p orbit!ls bec!#se
( ) ( ) 0 1 0 1 + + +
L
M . 'he conig#r!tion is A1sB
2
A2sB
2
A2p%B
1
A2p$B
1
A2p-B
1

10. 7ist the 6#!nt#m n#mbers 7) S) !n. ? or the ollowing terms s$mbols9
A!B
4
;542
AbB
3
P2
AcB
2
8342.
'he orm!t or the term s$mbols is
J
S
X
1 2 +
) where S is the spin 6#!nt#m n#mber)
A2S * 1B is the m#ltiplicit$) !n. J is the tot!l !ng#l!r moment#m 6#!nt#m n#mber. 'he "!l#e o 7
.etermines the letter s$mbol X !s ollows) 7 3 0 or S: 7 3 1 or P: 7 3 2 or 8: 7 3 3 or ,: 7 3 4
or ;: etc.
A!B
2
5
:
2
3
2
1 4
: 4

J S L
AbB
2 : 1
2
1 3
: 1

J S L
AcB
2
3
:
2
1
2
1 2
: 2

J S L
11. 8eri"e the gro#n. st!te term s$mbol or the ollowing conig#r!tion A5sB
1
A4.B
4
) i
gi"en th!t J 3 142.
( ) ( ) ( )
2
5
2
1
2
1
2
1
2
1
2
1
2 1 0 1 2 0

,
_

+ +
,
_

+ +
,
_

+ +
,
_

+ +
,
_

+
+ + + + + + +
S M
L M
S
L
< 1
2
5
2 1 2 +
,
_

+ S
'he term s$mbol is
<
8142. Dote th!t !ll 5 electrons !re #np!ire..
12. ;i"e the term s$mbol or 7i91s
2
2s
1
.
2
1
) 0 )
2
1
J L S
so the term is
2
S142. Dote th!t we !re onl$ consi.ering the #np!ire.
electron.
13. ,in. the tot!l !ng#l!r moment#m st!tes A7) M7B or two electrons) one p+t$pe !n. one
d+t$pe.
'he 6#!nt#m n#mber 7 m!$ h!"e "!l#es between 2 * 1 3 3 !n. 2 1 3 1.
7 3 3) M7 3 3) 2) 1) 0) 1) 2) 3 A= st!tesB
7 3 2) M7 3 2) 1) 0) 1) 2 A5 st!tesB
7 3 1) M7 3 1) 0) 1 A3 st!tesB
4
CHEM 342. Spring 2002. Problem Set #4. Answers.
'he tot!l n#mber o st!tes is = * 5 * 3 3 15.
14. When spin+orbit co#pling is l!rge) >#ssell+S!#n.ers co#pling !ils !n. jj+co#pling
m#st be #se.. Et in"ol"es irst co#pling the in.i"i.#!l spin !n. orbit!l moment! o the electrons
into in.i"i.#!l j "!l#es. 'hen) the 6#!nt#m n#mber J m!$ h!"e "!l#es between the s#m o the j
"!l#es o the in.i"i.#!l electrons !n. the !bsol#te "!l#e o the .ierence o these n#mbers.
2 1 2 1 2 1
)...) 1 ) j j j j j j J + +
. E there !re more th!n 2 electrons) then j1 is irst co#ple. to j2 to
in. ! J12. 'hen the tot!l !ng#l!r moment#m J is o#n. b$ co#pling j3 to ?12. ,in. !ll possible
"!l#es o J or
2
1
)
2
1
) 1
3 2 1
j j j
.
,irst) !.. j1 !n. j2 to obt!in
2
1
)
2
3
12
J
. 'hen !..
2
1
3
j
to the
2
3
12
J
st!te to obt!in
1 ) 2 J
: !n. !..
2
1
3
j
to the
2
1
12
J
st!te to obt!in
0 ) 1 J
. 'hereore)
0 ) 1 ) 1 ) 2 J
. Dote
th!t there !re two st!tes with J 3 1.
5