Chemistry 460 Spring 2013 Dr. Jean M.

Standard February 19, 2013

Quantum Chemistry Exam 1 Solutions

1.) (16 points) Explain or provide an example illustrating each of the following concepts. a . ) Born probability interpretation The Born probability interpretation states that the probability of finding a particle in the volume d" = dx dy dz between ( x , y , z ) and ( x + dx , y + dy , z + dz ) is given by " * ( x , y , z ) " ( x , y , z ) d# .

b . ) Normalization !

Normalization refers to the scaling of a wavefunction so that the total probability "sums" to 1. Since the wavefunction is expressed in terms of continuous variables, the sum becomes an integral, and the normalization requirement is

# " " d$
*

= 1,

and the integral is over all space. ! c . ) Orthogonal functions Two functions f and g are said to be orthogonal if the integral of their product (with one function as the complex conjugate) equals 0,

"f
d.) Tunneling !

g d# = 0 .

Tunneling is the penetration of the wavefunction into a classically forbidden region (i.e., a region in which E < V ).

2 2.) (22 points) A system is in a state described by the wavefunction " ( x ) = e of x from ! to +! . (k is a constant).
# ikx

for all values

a.) Show that this wavefunction is an eigenfunction of the ! linear momentum operator for the x coordinate. What is the eigenvalue? To show that the wavefunction is an eigenfunctions of the momentum operator, we must show that x " ( x ) = P " ( x) , p where P is a constant (the eigenvalue). For " ( x ) = e # i kx , application of the momentum operator gives ! x e" i kx = " i ! p ! d " i kx (e ) dx

= i 2 !k e" i kx x # ( x ) = " !k # ( x ) . p

So, we see that the wavefunction " ( x ) = e # i kx is an eigenfunction of the momentum operator with eigenvalue "! k . ! ! ! b . ) Determine how the energy eigenvalue E of the Schrdinger equation is related to the constant k for this system if the potential energy equals 0 for all x . To determine how E and k are related, the wavefunction can be substituted into the Schrdinger equation. Since the potential energy is zero everywhere, the Schrdinger equation is "
# ikx Substituting the form " ( x ) = e , !

!2 d 2 #( x ) = E #( x) . 2m dx 2

"

! 2 d 2 " ikx e = E e " ikx . 2m dx 2

Taking the second derivative on the left and simplifying yields ! " !2 " k 2e " ikx 2m

= E e " ikx

! 2 k 2 " ikx e = E e " ikx . 2m

3 2 b.) continued Since the function e " i kx is the same on both sides, we can divide this out to give !2k 2 = E. 2m

! Solving for the constant k, !

k =

2mE . !

4 and B which are Hermitian. Prove that their 3.) (16 points) Consider two operators A B =B A . Recall that product AB is Hermitian only if A and B commute; that is, only if A for an operator O to be Hermitian, it must satisfy the relation ! ! % % "( x ) * # ( x) ! ! ! " * ( x) ! O # ( x ) dx = O dx , $% $% !

&

& (

or in Dirac notation, ! # " O = " # O .

B satisfies the Hermitian relation, A We must show that the product operator !

&!
!

$%

B # ( x ) dx = " * ( x) A

B " ( x) ) & (A
$%

# ( x ) dx .

To begin, we can start with the left side of the Hermitian relation,

&

% $%

B # ( x ) dx , " * ( x) A

and then manipulate it to try to produce the right side of the Hermitian relation. In the integral above, recall that the operator nearest the function ! operates first to produce a new function. Therefore, B operates on " ( x ) to " ( x ) . Grouping terms, the integral above becomes produce the new function B

&

% $%

B # ( x ) dx . " * ( x) A

" ( x) . if the function on the right is B This looks like the left side of the Hermitian relation for the operator A gives Using the Hermitian character of!A

&

% $%

B # ( x ) dx = " * ( x) A

" ( x) # ( x ) dx ) (B ) & !( A " ( x) B ) # ( x) dx . & (A

$% % $% *

" ( x ) , the operator B in the The right side integral now looks like an integral with one function on the left, A , we have ! function, " ( x ) , on the right. Using the Hermitian property of B middle, and another "( x) ) & (A
$% % *

# ( x ) dx = B

A " (! x )) # ( x ) dx & (B !
$%

Equating the integral we started with to the right side of the equation above gives !

&
!

% $%

B # ( x ) dx = " * ( x) A

A " ( x) ) & (B
$%

# ( x ) dx .

5 3. continued B to be Hermitian is The relation for the product operator A

&

% $%

B # ( x ) dx = " * ( x) A

B " ( x) ) & (A
$%

# ( x ) dx .

From this, we see that the left sides of the previous two equations are the same; however, the right sides are the B =B same only if A !A ; thus, the product operator AB is Hermitian only if AB = BA .

* !

B to be Hermitian the relation is Carrying out the same proof using Dirac notation, for the product operator A B # " A = B " # A ! .

We may again start with the left side, manipulate it, and try to get the right side. The left side is ! B # " A = B # " A ,

gives where the only thing done on the right is to group terms. Using the Hermitian character of A ! B # " A = " B # A . ! , we have Then, using the Hermitian property of B ! ! B # " A = = " B # A A " # B .

B to be Hermitian is The relation for the product operator A ! B # = A B " # " A !

From this, we see that the left sides of the previous two equations are the same; however, the right sides are the B is Hermitian only if A B =B A ; thus, the product operator A B =B A . same only if A !

6 4.) (22 points) Determine the average value of the kinetic energy T for the one-dimensional particle in an infinite box. Recall that the wavefunctions of the one-dimensional particle in an infinite box have the form + = , . 2 $ n# x ' sin& ) , % L ( L 0, / 0* x* L 0 , x < 0, x > L 1

" n ( x)

where n is the quantum number and L is the width of the box. ! The average (or expectation) value of the kinetic energy T for the particle in an infinite box is defined as T =

L 0

* "n ( x) T " n ( x ) dx .

Note that the integration limits are 0 to L since the wavefunction for the particle in an infinite box is zero outside that range. We have also ! used the fact that the particle in a box wavefunction is normalized. Substituting the wavefunction into the expression for the average value yields T = =

)
2 L

L 0

# n" x & 2 sin% ( T L $ L ' L # n" x & # ! 2 sin% ( %* 0 $ L ' $ 2m

# n" x & 2 sin% ( dx L $ L ' d 2 & # n" x & ( sin% ( dx dx 2 ' $ L '

= * = * T =

!2 2 + 2m L !2 mL

# d 2 & # n" x & % 2 ( sin% ( dx 0 $ dx ' $ L ' L # n" x & # n 2 " 2 # n" x && sin% sin% ( + %* (( dx 0 $ L ' $ L2 $ L ''

# n" x & sin% ( $ L '

!2n 2" 2 mL3

L 0

# n" x & sin 2 % ( dx . $ L '

To evaluate the integral, we can look it up in a table. From the integral handout, !

" sin bx dx
2

x sin2bx # . 2 4b

n" By making the substitution b = , the integral becomes ! L

" sin bx dx
2

% 2 n$x ( x L # sin' *. 2 4 n$ & L )

Substituting, the average value expression becomes ! T

L $ 2n"x '!2n 2" 2 * x L = sin& )/ . , # 4 n" % L (.0 mL3 + 2

7 4. continued Evaluating at the limits yields T = = T = ' $ '! 2 n 2 " 2 *$ L L L # sin( 2 n" ) ) # & 0 # sin( 0) )/ 3 ,& ( % (. 4 n" 4 n" mL +% 2 !2n 2" 2 * L # 0 # 0 + 0/ , 3 . mL + 2 !2n 2" 2 . 2mL2

This result is the same as the energy eigenvalue. Since the potential energy inside the box equals 0, and the total energy is ! just the sum of the kinetic and potential energies, it makes sense that the average kinetic energy would equal the total energy.

8 5.) (24 points) In this problem, you will consider a particle trapped between an infinite wall (at x =0) and a finite potential barrier, shown below and defined by $ & & V ( x) = % & & ' ", 0, V0 , 0, x<0 0# x#L L< x#Q x>Q ( & & ). & & *

V=V0

II

III

IV

x=0

x=L

x=Q

a . ) Write down appropriate solutions for the Schrdinger equation in regions I, II, III, and IV for E < V0 . Assume that the particle starts in the trapped region (II); that is, it is impinging on the barrier (region III) from the left. If necessary, eliminate any terms in the solutions that would lead to unacceptable wavefunctions in the limit that ! x " # . Make sure that you define any constants that you use in defining your solutions. ! The general solutions for the wavefunctions in regions I-IV for the case E < V0 are

" I ( x) = 0 " II ( x ) = A sin kx + B! cos kx " III ( x ) = Ce #x + De $ #x " IV ( x ) = Fe ikx ,

where k for both regions II and IV and " for region III are defined as ! k ! = 2mE , ! 2m(V0 # E) !

" =

In region I, the wavefunction must equal 0 because the potential is infinite. None of the terms in these solutions need to infinity as x " # . !be eliminated because they go to !

9 5 . ) continued b . ) Apply the boundary conditions for the wavefunction at x = 0. the solution for the wavefunction in region II? The boundary condition at x = 0 is How does this simplify

" I ( 0) = " II ( 0) .
Substituting the forms of the wavefunctions leads to the equation ! 0 = A sin 0 + B cos 0 .

Since sin 0 = 0 and cos 0 = 1, the equation becomes ! ! 0 = B.

! Therefore, the solution for the wavefunction in region II simplifies to !

" II ( x ) = A sin kx .

! c . ) Apply the boundary conditions for the wavefunction and the first derivative at both x = L and x = Q . You should then take the ratio of the derivative and wavefunction equations at x = L and x = Q . This leads to two equations. Report the two equations, making sure to eliminate any constants that cancel, but do not do anything further with them. The boundary conditions at x = L are

" II ( L) = " III ( L )

and

"# II ( L) = "# III ( L) .

Substituting the forms of the wavefunctions and their first derivatives leads to the equations !

" II ( L) = " III ( L ) "& II ( L) = "& III ( L )

# #

A sin kL = Ce $L + De % $L Ak cos kL = $Ce $L % $De % $L .

Taking the ratio of these equations yields !

#"II ( L) # II ( L)

#"III ( L ) # III ( L )

10 5 c.) continued Substituting,

" Ce "L # De # "L kA cos kL = , A sin kL Ce "L + De # "L " Ce "L # De # "L
Ce
"L

( (

or k cot kL =

+ De

# "L

).

! The boundary conditions at x = Q are

" III (Q) = " IV (Q)

and "#III (Q) = "#IV (Q) .

Substituting the forms of the wavefunctions and their first derivatives leads to the equations !

" III (Q) = " IV (Q) "&III (Q) = "&IV (Q)

# #

Ce $Q + De % $Q = Fe ikQ

$Ce $Q % $De % $Q = ikFe ikQ .

Taking the ratio of these equations gives !

#"III (Q) # III (Q)

#"IV (Q) # IV (Q)

Substituting, !

" Ce "Q # De # "Q

Ce
"Q

( (

) )

+ De

# "Q

ikFe i"Q , Fe i"Q

or

" Ce "Q # De # "Q

Ce
"Q

+ De

# "Q

= ik .

! Summary The two equations found from matching at x = L and x = Q are

k cot kL =

" Ce "L # De # "L

Ce
"L

+ De

# "L

),

" Ce "Q # De # "Q

! Ce
"Q

+ De

# "Q

= ik .

These equations or their inverses are acceptable solutions. !

11 5 . ) continued d.) Explain, without solving the equations, how you would go about calculating the transmission coefficient T for this system. In this case, the transmission coefficient may be defined as T = Coefficient of wave in region IV Coefficient of wave in region II
2

In this case, the transmission coefficient is defined as ! T = F A

2

Therefore an expression for the ratio of coefficients F/A must be obtained. The two matching equations involving ratios from part (c) do not contain the coefficients F or A; therefore those equations may not be ! used directly to determine the transmission coefficient. Looking at the matching equations without taking ratios, we see that the wavefunction matching equation at x = L includes the coefficient A, A sin kL = Ce "L + De # "L , or A = Ce "L + De # "L . sin kL

In addition, the wavefunction matching equation at x = Q includes the coefficient F, ! Ce "Q + De # "Q = Fe ikQ , or F = Ce "Q + De # "Q . e ikQ

These two equations may be combined to obtain the ratio F/A, ! sin kL Ce "Q + De # "Q F = A e ikQ Ce "L + De # "L

( (

This equation includes the constants C and D. These may be determined using the ratios of the matching equations determined in part (c) by solving the two equations for the two unknowns C and D. Once the ! constants C and D are determined, they may be used to calculate the ratio F/A and thus the transmission coefficient.

12 5 . ) continued e.) Without solving any equations, sketch the expected form of the ground state wavefunction for the system given above for E < V0 . Qualitatively compare and contrast this wavefunction with the ground state wavefunction for the particle in a half-infinite well of the same width. Pay particular attention to the shape of the wavefunctions in the various regions.! Example graphs are shown below for the ground state wavefunctions for the system given in this problem (with a finite width barrier) and the particle in a half-infinite well. These wavefunctions were constructed using a box width of L=3 bohr for both systems, and a barrier width of 1.5 bohr for the finite barrier (i.e., L=3 and Q=4.5 bohr). In both cases the barrier height V0 is 4.5 hartrees. Ground State (n=1) This Problem
0.006 0.005 0.004 0.003

!
0.9 0.8 0.7 0.6 0.5

Half-Infinite Well

!(x)

!1(x)
0.0 2.0 4.0 6.0 8.0 10.0

0.4 0.3 0.2 0.1

0.002 0.001 0.000 -0.001

0.0 -0.1 0.0 2.0 4.0 6.0 8.0 10.0

x (bohr)

x (bohr)

In general, the shapes of the wavefunctions for the two systems are similar (note that the wavefunctions are not normalized, so the scale on the y-axis for each is arbitrary). Since the wavefunctions correspond to ground states, there are no nodes in the wavefunctions within the well or barrier regions. In addition, both wavefunctions exhibit similar tunneling behavior in classically forbidden region III. The differences between the two functions are most distinct in region IV. Here, the barrier in the halfinfinite well continues to infinity, whereas in this problem the finite width of the barrier means that the potential drops to 0 in region IV (for x>4.5 bohr in the example, or x>Q in general). The particle in the half-infinite well has a wavefunction that continues to die off monotonically to 0 as x increases. On the other hand, the particle trapped behind the finite barrier becomes free in region IV, and the wavefunction therefore exhibits free particle-like behavior in this region. The oscillations of the free particle-like wavefunction in region IV are low amplitude as a result of the small probability density for tunneling through the barrier. However, the oscillations in the wavefunction continue undamped with wavelength 2" for all x>Q . k