range of motion of the particle? Q15.6. The probability ... conditions? Q15.13.
Can the particles in a one-dimensional box, a square two-dimensional box, and a
.
Assignments for Chapter 15 Using Quantum Mechanics on Simple Systems Deadline: Before the end of the next chapter. 下一章結束日或之前繳交。
Questions on Concepts You hand in the answers to any 8 or more of the following questions: Q15.1 We set the potential energy in the particle in the box equal to zero and justified it by saying that there is no absolute scale for potential energy. Is this also true for kinetic energy? Q15.2 Discuss why a quantum mechanical particle in a box has a zero point energy in terms of its wavelength. Q15.3 How does an expectation value for an observable differ from an average of all possible eigenvalues? Q15.4 Is the probability distribution for a free particle consistent with a purely particle picture, a purely wave picture, or both? Q15.5 Why is it not possible to normalize the free‐particle wave functions over the whole range of motion of the particle? Q15.6 The probability density for a particle in a box is an oscillatory function even for very large energies. Explain how the classical limit of a constant probability density that is independent of position is achieved. Q15.7 Explain using words, rather than equations, why if , , , the total energy eigenfunctions cannot be written in the from , , . Q15.8 Can a guitar string be in a superposition of states or is such a superposition only possible for a quantum mechanical system? Q15.9 Show that for the particle in the box total energy eigenfunctions, / , is a continuous function at the edges of the box. Is 2/ sin / a continuous function of at the edges of the box? Q15.10 Why are standing‐wave solutions for the free particle not compatible with the
classical result v ? Q15.11 What is the difference between probability and probability density? Q15.12 Why are traveling‐wave solutions for the particle in the box not compatible with the boundary conditions? Q15.13 Can the particles in a one‐dimensional box, a square two‐dimensional box, and a cubic three‐dimensional box all have degenerate energy levels? Q15.14 Invoke wave‐particle duality to address the following question: How does a particle get through a node in a wave function to get to the other side of the box? Q15.15 Why is the zero point energy lower for a He atom in a box than for an electron? _____________________________________________________________________
Problems You hand in the solutions to any 15 or more of the following questions: P15.1 This problem explores under what conditions the classical limit is reached for a macroscopic cubic box of edge length a. An argon atom of average translational 0.500 m at 298 K. Use energy 3/2 is confined in a cubic box of volume the result from Equation (15.25) for the dependence of the energy levels on a and on the quantum numbers , , and . a. What is the value of the “reduced quantum number” for 298 K? b. What is the energy separation between the levels and 1 (Hint: Subtract from before plugging in numbers.) c. Calculate the ratio / and use your result to conclude whether a classical or quantum mechanical description is appropriate for the particle. P15.2 Calculate the expectation value for a particle in the state n = 3 moving in a one‐dimensional box of length . Is ? Explain your answer. P15.3 Normalize the total energy eigenfunctions for the three‐dimensional box in the interval 0 ,0 ,0 . P15.4 Is the superposition wave function for the free particle an eigenfunction of the
momentum operator? Is it an eigenfunction of the total energy operator? Explain your result. P15.5 Suppose that the wave function for a system can be written as √
and that
,
, and
are normalized eigenfunctions of the operator
with eigenvalues , 3 and 7 , respectively. a. Verify that is normalized. b. What are the possible values that you could obtain in measuring the kinetic energy on identically prepared systems? c. What is the probability of measuring each of these eigenvalues? d. What is the average value of that you would obtain from a large number of measurements? P15.6 Consider a free particle moving in one dimension whose probability of moving in the positive direction is three times that for moving in the negative direction. Give as much information as you can about the wave function of the particle. P15.7 Consider the contour plots of Problem P15.19. a. What are the most likely area or areas ∆ ∆ to find the particle for each of the eigenfunctions of depicted in plots a – f? b. For the one‐dimensional box, the nodes are points. What form do the nodes take for the two‐dimensional box? Where are the nodes located in plots a – f? How many nodes are there in each contour plot? P15.8 Evaluate the normalization integral for the eigenfunctions of for the particle in sin / using the trigonometric identity sin the box 1 cos 2 /2. P15.9 The function / 1 / is an acceptable wave function for the particle in the one‐dimensional infinite depth box of length . Calculate the normalization constant and the expectation values and . P15.10 What is the solution of the time‐dependent Schrödinger equation Ψ ,
for the
total energy eigenfunction 2/ sin 4 / in the particle in the box modal? Write / explicitly in terms of the parameters of the problem. P15.11
Derive an equation for the probability that a particle characterized by the quantum number is in the first 40. % 0 0.40 of an infinite depth box. Show that this probability approaches the classical limit as ∞. P15.12 It is useful to consider the result for the energy eigenvalues for the one‐dimensional box /8 , 1, 2, 3, as a function of , , and . a. By what factor do you need to change the box length to decrease the zero point energy by a factor of 275 for a fixed value of ? b. By what factor would you have to change for fixed values of and to increase the energy by a factor of 600. ? c. By what factor would you have to increase at constant to the zero point energy of a proton in the box? P15.13 /2 , are
Show that the energy eigenvalues for the free particle, consistent with the classical result 1/2 v . P15.14
a. Show by substitution into Equation (15.19) that the eigenfunctions of for a box with lengths along the , , and directions of , , and , repectively, are ,
,
, ,
b. Obtain an expression for
sin ,
,
sin
in terms of
sin ,
,
, and , , and .
P15.15 Calculate the wavelength of the light emitted when an electron in a one‐dimensional box of length 3.0 nm makes a transition from the 5 state to the 4 state. P15.16 A bowling ball has a weight of 15 lb and the length of the lane is approximately 60. feet. Treat the ball in the lane as a one‐dimensional box. What quantum number corresponds to a velocity of 5.0 miles per hour? P15.17 Using your result from P15.19, how many energy levels does a particle of mass in a two‐dimensional box of edge length have degeneracy of each level? P15.18
25
/8
? What is the
Are the eigenfunctions of for the particle in the one‐dimensional box also eigenfunctions of the momentum operator ̂ ? Calculate the average value of for the case 3. Repeat your calculation for 5 and, from these two results, suggest an expression valid for all values of . How does your result compare with
the prediction based on classical physics? P15.19 For a particle in a two‐dimensional box, the total energy eigenfunctions are ,
,
a. Obtain an expression for
,
sin in terms of
sin ,
, , and by substituting
this wave function into the two‐dimensional analog of Equation (15.19). b. Contour plots of several eigenfunctions are shown here. The and directions of the box lie along the horizontal and vertical directions, respectively. The amplitude has been displayed as a gradation in colors. Regions of positive and negative amplitude are indicated. Identify the values of the quantum numbers and for plots a – f.
P15.20 Calculate (a) the zero point energy of a CO molecule in a one‐dimensional box of length 1.00 cm and (b) the ratio of zero point energy to at 300. K. P15.21 Normalize the total energy eigenfunction for the rectangular two‐dimensional box, ,
,
sin
sin
In the interval 0 ,0 . P15.22 Generally, the quantization of translational motion is not significant for atoms because of their mass. However, this conclusion depends on the dimensions of the space to which they are confined. Zeolites are structure with small pores that we describe by a cube with edge length 1 nm. Calculate the energy of a H2 molecule with
10. Compare this energy to
at
300. K. Is s classical or a
quantum description appropriate? P15.23 Are the eigenfunctions of for the particle in the one‐dimensional box also eigenfunctions of the position operator ? Calculate the average value of for the case where 3. Explain your result by comparing it with what you would expect for a classical particle. Repeat your calculation for 5 and, from these two results, suggest an expression valid for all values of . How does your result compare with the prediction based on classical physics? P15.24 What are the energies of the lowest five energy levels in a three‐dimensional box with ? What is the degeneracy of each level? P15.25 In discussing the Boltzmann distribution in Chapter 13, we used the symbols and to indicate the degeneracies of the energy levels and . By degeneracy, we mean the number of distinct quantum states (different quantum numbers) all of which have the same energy. a. Using your answer to Problem P15.19a, what is the degeneracy of the energy level 5 /8 for the square two‐dimensional box of edge length ? b. Using your answer to Problem P15.14b, what is the degeneracy of the energy level 9 P15.26
/8
for a three‐dimensional cubic box of edge length ?
Show by examining the position of the nodes that Re and represent plane waves moving in the positive and negative Re directions, respectively. The notation Re[ ] refers to the real part of the function in the brackets. P15.27 Two wave functions are distinguishable if they lead to a different probability density. Which of the following wave functions are distinguishable from sin ? /2
a. sin b. c. cos d.
cos
, a constant /2 /2 sin
cos
√
√
, a constant
P15.28 Is the superposition wave function 2/ sin / sin eigenfunction of the total energy operator for the particle in the box? P15.29
/
an
The smallest observed frequency for a transition between states of an electron in a one‐dimensional box is 3.5 × 1014 s‐1. What is the length of the box? P15.30 Are the total energy eigenfunctions for the free particle in one dimension, /
and
/
, eigenfunctions of the
one‐dimensional linear momentum operator? If so, what are the eigenvalues? P15.31 Use the eigenfunction rather than sin cos to apply the boundary conditions for the particle in the box. a. How do the boundary conditions restrict the acceptable choices for and and for ? b. Do these two functions give different probability densities if each is normalized? P15.32 Consider a particle in a one‐dimensional box defined by 0, 0 and ∞, , 0. Explain why each of the following unnormalized functions is or is not an acceptable wave function based on criteria such as being consistent with the boundary conditions, and with the association of with probability. a.
cos
b. c.
d.
/
P15.33 Use your result from Problem P15.19 and make an energy level diagram for the first five energy levels of a square two‐dimensional box of edge length . Indicate which of the energy levels are degenerate and the degeneracy of these levels. P15.34 Calculate the probability that a particle in a one‐dimensional box of length is found between 0.18 and 0.22 when it is described by the following wave functions: a.
sin
b.
sin
What would you expect for a classical particle? Compare your results in the two case
with the classical result. _____________________________________________________________________
Web‐Based Simulations, Animations, and Problems W15.1 The motion of a classical particle in a box potential is simulated. The particle energy and the potential in the two halve of the box are varied using sliders. The kinetic energy is displayed as a function of the position , and the result of measuring the probability of detecting the particle at is displayed as a density plot. The student is asked to use the information gathered to explain the motion of the particle. W15.2 Wave functions for 1 5 are shown for the particle in the infinite depth box and the energy levels are calculated. Sliders are used to vary the box length and the mass of the particle. The student is asked questions that clarify the relationship between the level energy, the mass, and the box length. W15.3 The probability is calculated for finding a Particle in the infinite depth box in the interval 0 0.1 , 0.1 0.2 , , 0.9 1.0 for 1, 2, and 50. The student is asked to explain these results. W15.4 Contour plots are generated for the total energy eigenfunctions of the particle in the two‐dimensional infinite depth box, ,
,
sin
sin
The student is asked questions about the nodal structure of these eigenfunctions and asked to assign quantum number and to each contour plot. W15.5 The student is asked to determine if the normalized wave function 105
is an acceptable wave function for the particle in the infinite depth based on graphs of and / as a function of . The wave function is expanded in eigenfunctions of the total energy operator. The student is asked to determine the probability of observing certain values of the total energy in a measurement on the system. W15.6 The normalized wave function,
Ψ ,
/
sin
/
sin
2
| | With | | 1 is a superposition of the ground state and first excited state for the particle in the infinite depth box. Simulations are carried out to determine if , , and are independent of time for this superposition state.