FindingRoots

TheattempttofindanalyticalsolutionstoSchrodingersequationforsomeproblemsyields
transcendentalequationswhichmustbesolvedbyacombinationofgraphicaland
numericaltechniques.Mathcadisparticularlywellsuitedforsuchapplications.
SolvingSchroedingersequationfortheparticleintheboxwithaninternalbarrieryields
thetrancendentalequationf(E)shownbelow.Thisequationissolvedbyplottingf(E)vs
Etofindtheapproximatevaluesoftheboundenergystates.
Theboxis1bohrwideandthebarrieris0.1bohrthickandlocatedinthecenterofthebox.
Voisthebarrierheightinhartrees.

Vo := 100

Thebarrierthicknessinbohrs.

BT := .1

Leftbarrierboundaryinbohrs.

LB := .45

E := 0.05 , .1 .. 100

Vo E

f ( E) := tanh BT

2 ( Vo E)

Vo E

+ 2

sin LB

sin LB

) (

2 E cos LB

2 E

2 E

)2 + cos(LB

2 E

)2 ...

Foraderivationofthisformulasee:JohnsonandWilliams,Amer.J.Phys.1982,50,239244.

f( E)
0

0.05

20.05

40.05

60.05

80.05

Byinspectionofthegraphonecanseethattherearerootsatapproximately15,20,62,and
80.TheexactenergyisfoundwithMathcadsrootfunctionusingtheapproximateenergy
asaseedvalueasillustratedbelow.
E := 15

root ( f ( E) , E) = 15.43

E := 20

root ( f ( E) , E) = 20.29

E := 62

root ( f ( E) , E) = 62.24

E := 80

root ( f ( E) , E) = 81.07

Thisexercisecanbeextendedbynotingthatthisproblemcanalsobesolvedbynumerical
integrationofSchrodingersequation.Comparisionsofthissorthelparehelpfulinstrengthening
thestudentsunderstandingofthecomputationaltechniquesavailabletothequantumchemist.
BelowtheproblemissolvedbynumericalintegrationofSchroedingersequation.

xmax := 1

Integrationlimit:

lb := .45

Barrierboundaries:

Effectivemass: := 1
rb := .55

V0 := 100

V ( x) := if ( x lb) ( x rb) , V0 , 0

Potentialenergy:

NumericalintegrationofSchrodingersequation:

Given

Barrierheight:

Enterenergyguess:

E := 15.43

2 dx 2

( x) + V ( x) ( x) = E ( x)

:= Odesolve x , xmax

( 0) = 0

( 0 ) = 0.1

Normalizewavefunction:

( x)

( x) :=

xmax
2

( x ) dx

1.5

150

100

( x)

V ( x)
0.5

50

0.5
x

0.5
x