CHAPTER 3 The Schrédinger Equation and a Particle in a Box PROBLEMS AND SOLUTIONS 31. Evaluate g = A, where A and f are given below: Pp A f @ x o Cm © P-2e43 a ayy @ ee SQRT(x*) = £37 Ny xt 2 9 . fe ~2et3)dem Fae] =F BGty?t) , Baye ax? ay? Ferye') = bxytet +202 + 12y?? a2 ppeao re Af(@) =f @)T" [take As) = FO) [evaluate Af@) . Determine whether the following operators are linear or nonlinear: AFC) = SORF(®) [square f(2)] A f(x) = f*(x) [form the complex conjugate of f(x)] A f(x) =0 [multiply f (2) by zero] the reciprocal of f(x)] fax =0) In f(x) [take the logarithm of f(x)] 5152 Chapter 3 ‘An operator A is linear if A [c, f(x) + €,f,(2)] = e,4 f(a) + eA f(s) Equation 3: a Aly f@ +f] =[fOt+ehoy = AAP +2, HMO + ALO? CAL +e AAW) =¢ [AF +e [Aor #Ale fC) +¢,f,@)] Nonlinear. b. Alef) + F,0)] = 6) F@) + ey 2) AKO) + AAR) = FR) + 2) FAle A) +660] Nonlinear, « Alef) +e,f,09] =0 CALC) +64 hO) =o f)0+ ef) =0 = Ale, f(2) + 6:f,0)] Linear. a. Ale f,@ teh] = [4h +oF0)" AA + AL) = a + ao Alo A +e] Nonlinear. e Alef +e,f,@)] = of +50 ALC) + AL) Linear. f Ale, fix) +409] = Ine, 2) + 64,00] CAF (x) +A £02) = In fx) +6, In fe) #Ale LO +6,4,0)] Nonlinear.‘The Schrodinger Equation anda Particle in a Box 53 3-3. In each case, show that f(x) is an eigenfunction of the operator given, ‘ind the eigenvalue. A fa) os cosox wo 4 en © Bekes 0% we a Af@= Peoswx; eigenvalue= ~a* b. As@= we"; eigenvalue =i « Afey= — $20 30 (ot 20 ba) em d. Af@= 2 gate, cigenvalue = 6 ay 3-4. Show that (cosax)(cosby)(cosc2) is an eigenfunction of the operator, ax?” ay? az? ay" = ~a*(cosax)(cosby)(cosez) ~ b*(cos ax)(cosby)(coscz) ~c*(cos ax)(cos by)(cosc2) = -@ +B +2)(cosax)(cosby)(coscz) ‘The eigenvalue of the eigenfunction (cos.ax)(cosby)(coscz) is (a? +b? +c)54 Chapter 3 345. Write out the operator A? for e a #4 * bat © Gea Hint Be sue o include f(x) before carrying out the operations For all cases, we need to determine an expression for A? where #ro=4 [400] tf) Hf) dx? dx* “The operator Ais then a AAs@)= 4[ b. Alar] = (4 + [424 xf | cine a, xtf@ 2 -4 + feo PZ +2F2 4 27a) @ f(x) a 2 ast + 2x ‘de + Fx) +27 f(x) So A? is written as pena d 2 a Zp ak vtee @ oid PF) 4 afte ¢ po] = (Bak +1) [£2 afl + p03] a MFO) 4 PIO. gay oe = a ae + 2) +f@) So A? is written as ee é Fee tae Dat 3.6. In Section 3-5, we applied the equations for a particle in a box to the 2 electrons in butadiene. This simple model is called the free-electron model. Using the same argument, show that the length of hexatriene can be estimated to be 867 pm. Show that the first electronic transition is predicted to occur at 2.8 x 10" em", (Remember that hexatriene has six x electrons.) We assume that the x electrons move along a straight line consisting of three C=C bond lengths (3 x 135 pm), two C-C bond lengths (2 x 154 pm), and the distance of a carbon atom radius at cach end (2 x 77.0 pm) or a total distance of 867 pm. Because there are six x electrons in oneThe Selwédinger Equation and a Paticle in a Box 55 molecule, the first electronic transition occurs between the n = 3 and the n = 4 electronic states. Using Equation 3.21, the energy of this transition is, we AE=— ma (a? = 3°) (6.626 x 107 Js}? BOTT x 107 kg) (BOT x 10 = 5.61 x 10°”? J = 2.82 x 10 em! (16 - 9) alo 9 3-7. Prove that if ¥/(x) is a solution to the Schrédinger equation, then any constant times W(x) is also a solution Because A is a linear operator, Alew()] = cA W(x) = cEW(x) = Blew] and so cW(x), where c is any constant, is a solution. 3-8, Show that the probability associated with the state y, for a particle in a one-dimensional box of length a obeys the following relationships: l i even Prob(O en z cos dbx and so nl Bg ( Be 2 Now we use the Maclaurin series and the series expansion of ef (MathChapter J: 1(B) = 10) + BIO) + Fro + OUP) 1B) Therefore,58 Chapter 3 3411. Show that for all the states of a particle in a box. Is this result physically reasonable? ins [reowods 2 nx asin? gy a For any n, (x) = a/2. This result is physically reasonable and is discussed in detail in the text. 3-412. Show that (p) O for all states of a one-dimensional box of length a From Equation 3.37, [st cos ax ‘This result holds for any integer value of n 3413. Show that 0, = (GP) = (a)? for a particle in a box is less than a, the width of the box, for any value of n. Ifo, is the uncertainty in the position of the particle, could @, ever be larger than a? Use Equations 3.31 and 3.32 for (x) and (2°): W=5 wy) = (b =a(5 Foro, > a,‘The Schvodinger Equation and Particle in a Box 59 rn? — 6 > 12n?n? wr? > 12th? 46 ‘This inequality cannot be satisfied for any value of n, so.0, < a for all n 3-14, Using the trigonometric identity sin 29 = 2sin@ cos show that nmx nex, Lf". Qanx = cos ae =$ [ sin gy 315. Prove that f atemiedy=0 nO fl ereteas [os aes if sin Pay The integrals on the right side of this equation go over complete cycles of the cosine and sine funetions, and so both are equal to zer0 if n =f 0. If n = 0, the integral on the left side of this equation is a and the first integral on the right side of this equation is also a. 3-16. Using the trigonometric identity sina sin B = cos(a — B) — 5 costa + B) 2 show thatthe particle-in-a-box wave functions (Equations 3.27) satisfy the relation f VG) W,de mon (The asterisk in this case is superfluous because the functions are real.) Ifa set of Functions satisfies the above integral condition, we say that the set is orthogonal and, in particular, that ¥,,(x) is orthogonal to ¥,(x). If, in addition, the functions are normalized, then we say that the set is orthonormal. nm, bmx60 Chapter 3 (n—m)rx 1 (nt m)xx © (ama a cr 1 Tera MO ag sin me because sin Nor = 0 for integer values of NV. Note that ifm = m, ff econ if aif cos ge 1 and so the particle-in-a-box wave functions are orthonormal, 3-17. Prove that the set of functions eG) = (aye 0, dH, 82 is orthonormal (cf. Problem 3-16) over the interval ~a < x gin 22 We can separate ¥(x, y. z) into three one-dimensional wavefunctions X x), ¥(y), and Z(z) such that W(x, y, 2) = X()¥())Z(. These three one-dimensional wavefunctions have the same form and boundary conditions as the one we treated in Section 3-5, and so (as in Section 3-9) X(x) =A, sin = Yo 4 sin Z(@) = A, sin AE To normalize y/, we require that WEY DWE YD 124A) [s tax [ sin? Jn Problem 3-10, we leamed that f sin? “=a = $. Thus WO y.2)Y"C. I.) = 1 (A,4,49" (5) (3) (§) or 3-25. Show that (p) = 0 for the ground state of a particle in a three-dimensional box with sides of length a, b, and c x2) 58) w= [ads fay f devs y.0b0e. 9.0 sin AE) ax [sit ay [sat ae [ie 2LE (sn 2) ay [oo a x [sin ay [sin 22 (sn ME) ae64 Chapter 3 Each of these three sets of integrals has a multiplicative factor like f sin 27 egg" cos “=~ dx that results from taking a derivative. We have previously shown (Problein 3-14) that such an integral is equal to zero, and so we have (p) = 0 for a particle in a three-dimensional box. 3-26. What are the degeneracies of the first four energy levels for a particle in a three-dimensional box 1.5¢? with a = 2 [ni +n) +2.25n7 fe (=) os Energy level (7, n,, ,)__-DegeneracyE/(h?/8ma?) Ey, a1) 1 4.25 Ey, 21, D0, 2,0 2 7.25 Ex 220 1 10.25 Ew (1, 2) 1 Ey GLDGAD 2 12.25 Ey 10,22) 2 14 E, a3) 1 30.25 3-27. Many proteins contain metal porphyrin molecules. The general structure of the porphyrin molecule is ‘This molecule is planar and so we can approximate the x electrons as being confined inside ‘a square. What are the energy levels and degeneracies of a particle in a square of side a? The porphyrin molecule has 18 x electrons. If we approximate the length of the molecule by 1000 pm, then what is the predicted lowest energy absorption of the porphyrin molecule? (The experimental value is © 17000 em".) we ma? is singly degenerate for n, =n, and doubly degenerate for n, #1, (eh +m) @.57)‘The Schradinger Equation and a Particle in a Box 65 Energy level (mysm,) ___Degeneracy zy at) 1 Ey .DeQD 2 Ey @.2 1 Ey 6.00.3) 2 Ey 6.22.3) 2 Zu 00.4) 2 xy i) 1 Fa 6.22.4) 2 E, 9G.) 2 Because each energy level can hold 2 z-electrons, the lowest energy absorption of the porphyrin molecule will be that which excites an electron from the Ey, state to the E,, state. Then AE (nt +n — nt, — nt Sg a tama) (6.626 x 10-™ Js)" Hee pny 8 (9.11 x 107 kg) (1000 x 10° m) = 3.012% 10-5 Because E = hei, § = 1.52 x 10 cm". 3-28. The Schrddinger equation for a particle of mass m constrained to move on a circle of radius a is aby ~ 21 de where = ma? is the moment of inertia and 9 is the angle that describes the position of the particle around the ring. Show by direct substitution that the solutions to this equation are EY@) 0<<2n (0) = Ae” where n = -£(2/ £)'"/h. Argue that the appropriate boundary condition is ¥(@) use this condition to show that WO + 2m) and wae Poor n=0, 41, £2, ‘Show that the normalization constant A is (27), Discuss how you might use these results for a free-electron model of benzene. ‘We can write the differential equation as 2E1 a W@) =0 Substituting ¥(0) =66 Chapter 3 orn = +(21E)""/h, Because the particle is moving in a circle, it must return to any designated point after traveling 2x radians: Y(@) = W(@ + 2m). Then eit = ener) taem 1 = cos2rn +i sin 2am ‘This is true only if m is an integer. In that case, ‘To normalize (x), we require that ‘There are six x electrons in benzene. If we model the electrons of a benzene molecule as described above, there will be two electrons in each of the three energy levels m =0 and + 1. The first electronic transition would be an = | > n = 2 transition, and the frequency associated with this transition would be given by the expression h 2 42) gat 3-29. Set up the problem of a particle in a box with its walls located at —a and +a. Show that the energies are equal to those of a box with walls located at 0 and 2a. (These energies may be obtained from the results that we derived in the chapter simply by replacing a by 2a.) Show, however, that the wave functions are not the same and in this ease are given by nodd Does it bother you that the wave functions seem to depend upon whether the walls are located at ‘ta or 0 and 2a? Surely the particle “knows” only that it has a region of length 2a in which to ‘move and cannot be affected by where you place the origin for the two sets of wave functions. ‘What does this tell you? Do you think that any experimentally observable properties depend upon ‘where you choose to place the origin of the x-axis? Show that 0,0, > fi/2, exactly as we obtained in Section 3-8. ‘The general solution of the Schrédinger equation for a particle in a one-dimensional box is (Section 3-5) (2mE)'? (x) = Acoskx + Bsinkx Wx) = Acoske + Bsi 7‘The Schrddinger Equation and a Particle in a Box 67 ‘We have the boundary conditions y(—a) = ¥(a) = 0, so W(-a) = Acos(—ka) + B sin(-ka) = A coska ~ B sinka = 0. and W(a) = Acos(ka) + Bsin(ka) = Acoska + Bsinka =0 Adding and subtracting these two equations gives Acoska=0 and Bsinka =0 ‘The general solution to these equations is to set. 2a where n = 1,2,... and to satisfy the boundary conditions by setting B = 0 when n is odd and A = 0 when n is even. Thus k W,(0) = Bsn" even = Acos nod The normalization constants A and B are both equal to a~', We find E through the defined variable k: Qmey? i Wen? 32m When we solved the Schrodinger equation for the boundary conditions y-(0) = y-(2a) = 0 (Section 3-5), we found hen? * Bra(2a)? 2, Which is the same result as that for & box with walls located at ta. Realize that the wave functions are independent of where the walls are located; however, how we define our coordinate system will change the way we express the wave function mathematically. No experimentally observable properties depend upon how we define our coordinate system - the coordinate system is a purely hypothetical construct which does notimpact any observable system. Since a, and, are observable properties, 9,0, > h/2.as in Section 3.8. 3-30. Fora particle moving in a one-dimensional box, the mean value of x is a/2, and the mean square deviation is o2 = (a7/12){1 — (6/x7n*)], Show that as n becomes very large, this value agrees with the classical value. The classical probability distribution is uniform, O i(—2mE)'"/h and fim 00) = Jig eT" diverges. Therefore, E must be positive. Using Equation 3.1 for the momentum operator, we find p dy, 4 ty ge Puy = 0 = in (aye) = —PhkA,e = hae = hha (x) ~in-® (Ae) =P hkAe™ = ~hkAy ky (2) For a free particle, all energy is kinetic energy. The possible values of the momentum of a free particle are hk and —hk. Using E = p?/2m, we find that (bak? we mn Finally, CO (8) = (Aie™) (Aye) = Ata, = |A,P = constant WEED = (Aze") (Ae) = AzA, = [A,)* = constant Since W*(x)y/() is a constant, the particle is equally likely to be found anywhere along the x axis. Thus, there is an infinite uncertainty in the location of the particle. This is consistent with the Uncertainty Principle because the momentum of the particle is known exactly (0, 3-33. Derive the equation for the allowed energies of a particle in a one-dimensional box by assuming that the particle is described by standing de Broglie waves within the box. The de Broglie relationship is (1.12) Because the waves are standing waves, an integral number of half-wavelengths will fit into the box, mh nh 2 2p Solving for p gives and the corresponding energy isChapter 3 3-34. We can use the Uncertainty Principle for a particle in a box to argue that free electrons cannot exist in a nucleus. Before the discovery of the neutron, one might have thought that a nucleus of atomic number Z and mass number A is made up of A protons and A — Z electrons, that is, just enough electrons such that the net nuclear charge is +-Z. Such a nucleus would have an atomic number Z and mass number A. In this problem, we will use Equation 3.41 to estimate the energy of an electron confined to a region of nuclear size. The diameter of a typical nucleus is approximately 10" m, Substitute a = 10" m into Equation 3.41 and show that o, is, o,, = 3 x 107 kgm. Show that Bosc E Im 5x 10° = 3000 MeV. vere iions of lecton vols (MeV) isthe common nla physics unit of ene Tis observed ‘Xpesimently tha electrons ented fom nll as pradaton have energies of only afow MEV. which is far less than the energy we have calculated above. Argue, then, that there can be no free electrons in nuclei because they should be ejected with much higher energies than are found experimental. sk _ nk oe ean Forn = 1 anda = 10" m, = SEBO 9M gms! 2(1 x 107" m) F st (Problem 3-23) and in this case we BX 107 kgm. s 1)? 209.11 x 10" kg) Because no nuclei emit electrons with energies on the order of 1000 MeV, we assume such electrons do not exist in nuclei; therefore, there can be no free electrons in nuclei. (Electrons with energies of only a few MeV are the result of a neutron decaying into a proton and an electron in the nucleus.) 5 x 10" J = 3000 MeV 3-35. We can use the wave functions of Problem 3-29 to illustrate some fundamental symmetry properties of wave functions. Show that the wave functions are alternately symmetric and antisymmetric or even and odd with respect to the operation x > —x, which is a reflection through the x = 0 line. This symmetry property of the wave function is a consequence of the symmetry of the Flamiltonian operator, as we now show. The Schrédinger equation may be written as AG), (2) = Ev) Reflection through the x = O line gives x + —x and so AU-2,(-8) = E,Wy(-X)‘The Schebdinger Equation and a Particle in a Box 75 Now show that A(x) = H(—x) (ic. that H is symmetric) for a particle in a box, and so show that AQ, (-9) E,Y(—¥) ‘Thus, we see that, (x) is also an eigenfunction off belonging to the same eigenvalue E,. Now, ifenly one eigenturction i associated with each eigenvalue (te site is nondegenerate), beh argue that, (2) and ¥,(-x) must differ only by a multiplicative constant [ie that Y,(3) = e¥,(~3)] By applying the inversion operation again to this equation, show that c = 41 and that all the wave functions must be ether even or odd with respect o reflection though the x = O line because the Hamiltonian opereioris symmetric. Thus, we se tat the symmetty ofthe Hamiltonian operator influences the symmetry ofthe wave functions. A general stady of symmetry uses group theory, and this example is actually an elementary application of group theory to quanturt-methanical problems. We will study group theory in Chapter 12. Consider the wavefunctions found in Problem 3-29. For odd Jv and the wavefunctions for even n are antisymmetric function of x. i wed? A(x) = Im dx = onan BON = aaa Now we have shown that E,,(—x) = H(x)¥,(—x) = A(x)y,(2). Ifthe state is nondegenerate, V,(-X) = eV, (2). Repeating the operation, we find V(x) = c¥, (2) = PY, (2) which leads to the conclusion that ¢ = +1 and consequently to the conclusion that all (x) are either even or odd with respect to reflection through the x = 0 line. Thus the symmetry of the Hamiltonian influences the symmetry of its eigenfunctions (assuming a nondegenerate system).