5.

61PhysicalChemistry 24PauliSpinMatrices Page 1

PauliSpinMatrices
Itisabitawkwardtopicturethewavefunctionsforelectronspinbecause
theelectronisntspinninginnormal3Dspace,butinsomeinternaldimension
thatisrolledupinsidetheelectron. Wehaveinventedabstractstates
andthatrepresentthetwopossibleorientationsoftheelectronspin,
butbecausethereisntaclassicalanalogforspinwecantdrawand
wavefunctions. Thissituationcomesupfrequentlyinchemistry. Wewill
oftendealwithmoleculesthatarelargeandinvolvemanyatoms,eachof
whichhasanucleusandmanyelectronsanditwillsimplybeimpossiblefor
ustopicturethewavefunctiondescribingalltheparticlesatonce.
Visualizingone-particlehasbeenhardenough!Inthesesituations,itismost
usefultohaveanabstract wayofmanipulatingoperatorsandwavefunctions
withoutlookingexplicitlyatwhatthewavefunctionoroperatorlookslikein
realspace. ThewonderfultoolthatweusetodothisiscalledMatrix
Mechanics(asopposedtothewavemechanicswehavebeenusingsofar).
Wewillusethesimpleexampleofspintoillustratehowmatrixmechanics
works.
Thebasicideaisthatwecanwriteanyelectronspinstateasalinear
combinationofthetwostatesand:
c

+c

Notethat,fornow,weareignoringthespatialpartoftheelectron
wavefunction(e.g.theangularandradialpartsof).You mightaskhowwe
canbesurethateverystatecanbewritteninthisfashion.Toassure
yourselfthatthisistrue,notethatforthisstate,theprobabilityoffinding
2
2
theelectronwithspinup(down)is c

(c

). Iftherewasastatethat
couldnotbewritteninthisfashion,therewouldhavetobesomeotherspin
state,,sothat
c

+c

+c

2
Inthiscase,however,therewouldbeaprobability c

ofobservingthe
electronwithspin whichweknowexperimentallyisimpossible,asthe
electrononlyhastwoobservablespinstates.
Thebasicideaofmatrixmechanicsisthentoreplace the wavefunction
with a vector:
1
5.61PhysicalChemistry 24PauliSpinMatrices Page 2
|c

|
c

+c

|
\
c

Notethatthisisnotavectorinphysical(x,y,z)spacebutjustaconvenient
waytoarrangethecoefficientsthatdefine. Inparticular,thisisanice
waytoputawavefunctionintoacomputer,ascomputersareveryadeptat
dealingwithvectors.
Now,ourgoalistotranslateeverythingthatwemightwanttodowiththe
wavefunctionintosomethingwecandotothevector . Bygoingthrough
thisstep-by-step,wearriveatafewrules
Integrals are replaced with dot products.Wenotethattheoverlap
betweenanytwowavefunctionscanbewrittenasamodifieddotproduct
betweenthevectors. Forexample,if d

+d

then:
1 0 0 1

* *

* *

* *

* *

*
d =d

d +d

d +d

d +d

d
* *
=d

+d

|c |
=
(
d
*
d
*
)

|

\
c

i
Where,onthelastline,wedefinedtheadjointofavector:

|x
1
|
* *
|

(
x
1
x
2
)
.
\
x
2
Thus, complex conjugation of the wavefunction is replaced by taking the
adjoint of a vector. Notethatwemusttakethetransposeofthevector
andnotjustitscomplexconjugate.Otherwisewhenwetooktheoverlapwe
wouldhave(column)x(column)andthenumberofrowsandcolumnswould
notmatch.
Theserulesleadustonaturaldefinitionsofnormalizationandorthogonality
ofthewavefunctionsintermsofthevectors:
2

*
(

*
)
|
c
c

|
|
d =1 i = c c = c

+ c

=1
\

and
2
5.61PhysicalChemistry 24PauliSpinMatrices Page 3
|c |
d =0 =
(
d d
) |
=d c +d c =0 i

*
c

*

*

Finally,wedliketobeabletoactoperatorsonourstatesinmatrix
mechanics,sothatwecancomputeaveragevalues,solveeigenvalue
equations,etc. Tounderstandhowweshouldrepresentoperators,wenote
thatinwavemechanicsoperatorsturnawavefunctionintoanother
wavefunction. Forexample,themomentumoperatortakesonewavefunction
andreturnsanewwavefunctionthatisthederivativeoftheoriginalone:
x x ( )
p

d
( )
dx
Thus,inorderforoperatorstohavetheanalogousbehaviorinmatrix
mechanics,operatorsmustturnvectorsintovectors. Asitturnsoutthisis
themostbasicpropertyofamatrix:itturnsvectorsintovectors. Thuswe
haveourfinalrule:Operators are represented by matrices.
Asanillustration,the S

z
operatorwillberepresentedbya2x2matrixin
spinspace:
|? ?|
S

z
S
z

|
\
? ?

Wehaveyettodeterminewhattheelementsofthismatrixare(hencethe
questionmarks)butwecanseethatthishasalltherightproperties:vectors
aremappedintovectors:
|? ?|
|c

| |c

' |
S

z
=
|
|
=
|
\
? ?

\
c

\
c

'

andaveragevaluesaremappedintonumbers

*
S

z
d
(
c

*
c

*
)
|? ?
|
|

|
c
c

|
|

\
? ?

Now,theonechallengeisthatwehavetodeterminewhichmatrixbelongsto
agivenoperatorthatis,weneedtofillinthequestionmarksabove. Asan
exercise,wewillshowhowthisisdonebyworkingoutthematrix
representationsof S

2
,S

z
, S

x
and S

y
.
Wellstartwith S

2
. Weknowhow S

2
actsontheandwavefunctions:
3 3
S

2
=
2
S

2
=
2

4 4

5.61PhysicalChemistry 24PauliSpinMatrices Page 4

Nowrepresent S

2
asamatrixwithunknownelements.
|c d|
S
2
=
|
\
e f

Inwavemechanics,operating S

2
ongivesusaneigenvalueback,because
isandeigenfunctionof S

2
(witheigenvalue
4
3

2
). Translatingthisintomatrix
mechanics,whenwemultiplythematrix S
2
timesthevector

,weshould
getthesameeigenvaluebacktimes :
S

2
=
3

2
S
2

=
3

4 4
Inthisway,insteadoftalkingabouteigenfunctions,inmatrixmechanicswe
talkabouteigenvectorsandwesaythat

is an eigenvector of S
2
.
Wecanusethisinformationtoobtaintheunknownconstantsinthematrix
S
2
:
2
3
2 2
3
2
|c d| |1|
2
|1|
S

= S =
| |
=
4
3

|
4 4
\
e f
\
0
\
0

|c| |
3

2
|

|
=

4
|
e
\ \
0

so
c=
3

2
e=0
4
Operatingon
3 3
2
|c d||0|
3
2
|0|
S

2
=
2
S
2
=
| |
=
4

|
4 4
\
e f
\
1
\
1

|d| | 0 |

|
=

3
2 |
\
f
\4

Thus:
d=0 f =
3

2
4
Sofor S
2
wehave
S
2
=
3

2
|

1 0|
|
4
\
0 1

Wecanderive S
z
inasimilarmanner.Weknowitseigenstatesaswell:
S

z 2 z 2
Sothatthematrixmustsatisfy:

5.61PhysicalChemistry 24PauliSpinMatrices Page 5

|c d| |1| |1|
S

z
=
| |
=
2 |
2
\
e f
\
0
\
0

|c| |
2

|
=
|
\
e
\
0

whichgivesus
c= e=0
2
Analogousoperationsongive
|c d| |0| |0|
S

z
=
| |
=
2 |
2
\
e f
\
1
\
1

|d| | 0 |

|
=

|
\
f
\

2
d=0 f =
2
Compilingtheseresults,wearriveatthematrixrepresentationof S :
z
|1 0 |
S
z
=
|
2
\
0 1

Now,weneedtoobtain S
x
and S
y
,whichturnsouttobeabitmoretricky.
Werememberfromouroperatorderivationofangularmomentumthatwe
canre-writethe S and S intermsofraisingandloweringoperators:
x y
1 1
S
x
= (S
+
+S
-
) S
y
= (S
+
S
-
)
2 2i
whereweknowthat
S

=c S

=0 and S

=c S

=0
+ + +
wherec
+
andc
-
areconstantstobedetermined.Thereforefortheraising
operatorwehave
S

=c
|c d||0|
=
|c
+
|
S

=0
|c d||1|
=
|0|
+ + | | | + | | |
\
e f
\
1
\
0
\
e f
\
0
\
0

d=c f =0 c=0 e=0

+
Andfortheloweringoperator
|c d| |1| |0| |c d||0| |0|
S

=c

| |
=
|
S

=0
| |
=
|
\
e f
\
0
\
c
\
e f
\
1
\
0

c=0 e=c d=0 f =0

Thus
|0 1| |0 0|
S
+
=c
+ |
S
-
=c
|
\
0 0
\
1 0

=
5.61PhysicalChemistry 24PauliSpinMatrices Page 6
Thereforewefindfor S and S
x y
1|0 c | 1| 0 ic |
S
x
=
1
2
(S
+
+S

) =

+
|
S
y
=
2
1
i
(S
+
S

) =

+
|
2
\
c

2
\
ic

Thus,wejustneedtodeterminetheconstants:c
+
andc
-
. Wedothisby
usingtwobitsofinformation. First,wenotethat S
x
and S
y
areobservable,
sotheymustbeHermitian.Thus,
*
1 1
*
| 0 c | |0|
| | 0 c ||1|
|

*S

x
d =
(

*S

x
d
)
(1 0)

1
c
2
0
+
|
1
|
=

(0 1)

1
c
2
0
+
|
0
|
|
\2 \
\ \2 \

*
c =c
+
Thisresultreducesourworktofindingoneconstant(c
+
)intermsofwhich
wehave
1| 0 c
+
| 1| 0 ic
+
|
S
x
=
* |
S
y
=
* |
2
\
c
+
0

2
\
ic
+
0

Notethat S and S havetheinterestingpropertythattheyareequalto

x y
theiradjoints:

1| 0 c | 1| 0 c |
S
x

=
*
+
|
=
*
+
|
=S
x
2
\
c
+
0

2
\
c
+
0

1| 0 ic | 1| 0 ic |
S
y

=
*
+
|
=
*
+
|
=S
y
2
\
ic
+
0

2
\
ic
+
0

Thispropertyturnsouttobetrueingeneral:Hermitian operators are

represented by matrices that are equal to their own adjoint. Theseself-
adjointmatricesaretypicallycalledHermitianmatricesforthisreason,and
theadjointoperationissometimescalledHermitianconjugation.
Todeterminetheremainingconstant,weusethefactthat S
2
= S
x
2
+S
y
2
+S
z
2
.
Plugginginourmatrixrepresentationsfor S
x
, S
y
, S
z
and S
2
wefind:
3
2
|1 0|
2
|1 0 | |1 0 | 1| 0 c
+
| | 0 c
+
| 1| 0 ic
+
| | 0 ic
+
|
=
| | |
+
* | * |
+
* | * |
4
\
0 1

4
\
0 1
\
0 1

4
\
c
+
0
\
c
+
0

4
\
ic
+
0
\
ic
+
0

2 2

2
|1 0| c |1 0| c |1 0|
+ +
=
|
+
|
+
|
4
\
0 1

4
\
0 1

4
\
0 1

2 2
3
2

2
c
+
c
+
= + +
4 4 4 4
2
2
c
+
c =
+
5.61PhysicalChemistry 24PauliSpinMatrices Page 7
whereonthelastline,wehavemadeanarbitrarychoiceofthesignofc
+
.
Thuswearriveatthefinalexpressionsfor S and S
x y
|0 1| |0 i |
S
x
=
|
S
y
=
|
2
\
1 0

2
\
i 0

Insummary,then,thematrixrepresentationsofourspinoperatorsare:
|0 1| |0 i| |1 0 |
2
3
2
|1 0|
S
x
=
|
S
y
=
|
S
z
=
|
S =
|
2
\
1 0

2
\
i 0

2
\
0 1

4
\
0 1

Givenourrepresentationsof S
x
, S
y
and S
z
nowwecanwork outanyproperty
welikebydoingsomelinearalgebra. Forexample,wecanworkoutthe
commutatorof S and S :
x y
|0 1||0 i| |0 i||0 1|
S , S (=S S S S =

x y

x y y x | |

| |
2
\
1 0

2
\
i 0

2
\
i 0

2
\
1 0

2
|0 1||0 i| |0 i | |0 1|(
=
| |

| |(
4
\
1 0
\
i 0
\
i 0
\
1 0

|i 0| |i 0|
(

2
|i 0|
=
|

|(
=
|
4
\
0 i
\
0 i

2
\
0 i

S
x
, S
y

(=iS
z
Itiscomfortingtoseethatthematricesthatrepresenttheangular
momentumoperatorsobeythecommutationrelationsforangularmomentum!
Itissimilarlypossibletoworkouttheeigenvaluesof S

2
,S

z
and S

x
by
computingtheeigenvaluesof S
x
, S
y
and S
z
;averagevaluescanbeobtained
bytaking(row)*x(matrix)x(column)products. Wearethusinapositionto
computeanythingwewantfortheseoperators.Asitturnsout,anyoperator
inthis2x2spacecanbewrittenasalinearcombinationof S
x
, S
y
, S
z
and S
2
.
So,insomesense,wenowhavealltheinformationwecouldpossiblywant
aboutspin-systems.
InhonorofPauli,itisconventionaltodefinethedimensionlessversionsof
S
x
, S
y
, S
z
(i.e.matriceswithouttheleadingfactorof / 2)asPauliSpin
matrices:
|0 1| |0 i| |1 0|

|
\
1 0
\
i 0
\
0 1

OneofthereasonsthePaulispinmatricesareuseful(orequivalentlythe
matrixrepresentationsof S
x
, S
y
and S
z
)isthattheyarethesimplest
5.61PhysicalChemistry 24PauliSpinMatrices Page 8
possibleplacetopracticeourskillsatusingmatrixmechanics. Wewillsee
lateronthatmorecomplicatedsystemscanalsobedescribedbymatrix-
vectoroperations. However,inthesecasesthematriceswillhavemany
moreelementssometimeseveninfinitenumbersofelements! Therefore,it
isbesttogetsomepracticeonthesesimple2x2matricesbeforetakingon
themorecomplicatedcases.