50 Makchatr8 and few n= In —2)-- where nis factorial or Fist, we demons that pe is normalized by showing that fo" poh = [meade =an( =r) [ve m_)" tht (20bgT" -*(aiz) (GP) (ai) PZ)" ‘av Using Equation B12, we write 1-7. Use the Maxwell-Bolumann disuibuton in Problem B-6 to determine the average kinetic ‘nergy of sg phase molecule a «fanedon of temperature, The necessity itera sien a Problem B-6, ‘Kinetic energy, KE, is defined as KE = Jr? so (KE} = mo) Using Equation B.13, we write ; wate (seq) [eevee The Schrédinger Equation and a Particle in a Box PROBLEMS AND SOLUTIONS 34. Baste gm A fwhere A mae po © soer : b 2) « [[e-mena Fay seca Gest 20 4 12ey'd ‘ ie 3-2, Determine wheter the following operators ar linear woe: 4 fe) = SQRYU) (squae F)] b. A sce) = °C) ortho complex conjugate off) A fce)=0 (mally f(s) by xr] a. Af) = {fe lake be recipeal of fx) Aste) = f(0) (erate F(0) atx = 0) 1. Af(e)=In f(a) (ake the ogni of 6] st52 Anopertor A sina if Af, 8) +6, f(2)] = 6A 10) + 6,4 (2 (quation 3. = Alghero] = [ese +ehtoF EC +26, he loa har? Aft eA =e, hel +e (neo. Fale hO +e f03] Nonlin & Al hOrehol| ech +eg HO) ehh) +6 Mla) =6 Je) + ef) Ale hd +460] Nontines . Ale hie +e,f00)]=0 Ania) +A KO)= oh +e =0 = Aled 400] Linea a AL, H+ 500) = [hl +f] Aft bok = Fi +7 Fale hed +4 he] Nontnea, . Afeher +e hia] =e hi +660) Af ted heed Lines. t Ale,ster +e, 00] = Infe, 5000-46609] Af) -+ed (0) =e, f8) + l8 KO) FA fehOd + qh] Nonlinear. TheStreet Bo 3-3. Ineach ease, show that f(x) i an eigenfunction ofthe opeatr giver, Find the eigenvalue i 10 # oF coon aye a eye ee ay “ a Ape Pleo I PLOY 8 ePeosers eigemalue = 0 pt = 4S oe sigs ey, te ee) = 2D AO grea ete) igneate ea Be 3 ipa = BEY ore . 4 Ape = EE 60d dere =6 2-4, Show that (osas)(cos by) (core) ean eigenfunction ofthe operator, aoe e Oost ay tae ‘which is called the Lapscian operator, Hlasaneasby onset), Pooeanconby.cnct oF —z =~" caran\canby one) =H onan .cnbycnee) ‘¥ (eosany(cosby cores ~€eosaxy(cosby (e082) (a! +B + Mcosax)(eosby (cose) ‘The eigevale ofthe eigenfunction cos ax)(cosby) eoscz) is +b +e. EEE 5354 3-5, Write ou the operator 4 for e a e = bo fae « Sota a & aw ine: Be sure ioclade F()belore ery out te operations oral eases, we noe to determine an expression for 4 wheve [are] ‘The operator Ais then . sea]= (d+) [LE +s] £10 A FLO HO. Fe) 42K ‘So A? is written as bye Brad sine ‘ [aves] = (aed 41) [LER ells 40) 4.210) 4 ®IO., pep a ae ae So A? is writen ws “af anf ara et ‘3.6, In Section 3-5, we spl the equation for apace in «box to the = electrons in butadiene “This simple mode cll the free-electron model Using te sme argument, show thatthe length ofhexatrien ca be estimated to be 867 pm. Show that Ie fst electronic wanton is predicted to occur 2.8 % 10 em! (Remember that hexane letrons) ‘We assume that the elecwons move along a sraght line consisting of tree C=C bond lengths (Gx 135 pm), two C-C bond lengths (2 > 154 pm), and the distance of acarbon atom radius at tach end (2% 77.0 pm) oF a tol distance of 867 pm. Because there are sx elecons ia ne _ molecule, the ist electronic tanson occurs between then = 3 andthe = 4 electronic states. ‘Using Eauation 3.2, the energy ofthis ranston is a ae A na = (662611 I iggy BOTT 10 aT 10 1 x 10-1 = 282 10cm" 3-7, Prove hati (e) ia soation tothe Schrnger equation, then any constant times W(x) i a9 ‘soliton Because i linear operator, Atewayl=efiven (2) = Blowtadl isany constants soton Jen one dimessonal box of 3-8, Show that he probability asiciated with he ste, For apa length a obeys the Following relationships Prob(O =x h/2 exactly as we obtained in Section 3-8 x the two sts of wave fanetions ‘The general solution of te Schrbinger equation for particle ina one-dimensional box is (Section 3-5) ney Vis) = Aconks + Bsinks k= OE Te SiagCquon anda Paina foe 67 ‘We have the boundary conditions ¥(-a) = Wa) = 0.90 (a) = Acos(Ha) + Bsing~ka) = Acoska ~ Bsinka snd (a) = Acos(ka) + Bsintha) = Acosta + Bsinka=0 Adding and subeacing these two equations gives Acosta =0 and Bsinka = ‘The general salution to thee equations isto st where n= 1, 2,.-. and wo sasisy the boundary conditions by seting B= O whea mis od and A= O when even. Thos 9,0) = BsinZ even Aco med 2a “The normalization constants A and B are bth equal oa". We find & through the defined variable |When we solved the Seiciingerequition forthe boundary conditions (0) = (2a) (Seeton 3-8), we found wee Tnay hich is the same result stat for a box wth wale cad at bo, Realize tht the wave fonctions te independent of whore the walls ae locate: however, how we define our eoontinate system wil change the way We expres the wave function mathematically, No experimentally observable Properties depend ypon how we dein or coordinate system - he coordinate system isu purely hypothetical constut which des nocipect any obsenablesystem, Since 9, and, ae observable properties, 0, > A/2 8 in Section 3. 3-80, For particle moving none dimensional bes, the mean vale of #8 /2, and the mean square {/2|1 — (6). Show tat arm becomes very large, this value sprees swith the cassia value. The casial probability disubuton i uniter, t podem lax Oenea ° cherie Ctasially,68 Cher For the park 3-31, This problem shows that he intensity of a wave i proportional tothe square of ts amplitude, Figure 3.7 lastates the geometry ofa vibraing sting. Because the velocity at any point ofthe stings Ou, the kets energy ofthe entre sing whore isthe linear mass density ofthe sting, The potential energy is fund by considering the inereae of length ofthe small ae PQ of length ds in Figure 37. The segment ofthe sng slong that ar as increased its ng rom dtd, Therefor the potential energy associated with his va [rasa where 7 isthe tension nthe string. Using the fact that (ae) = (a) + C)?, how that feel} rf (@)« For small displacements. The teal energy ofthe vibrating sng isthe sum of K and V and so eb f(a) ersl Ge v v Fieune 37, ‘he geeety of bang eng, ‘We showed in Chapter 2 (Equations 2.23 trough 2.25) that he mth normal mode canbe waiten in the form ated cost +) sin ‘where, = m/l. Using his equation show that Kx EEE prion +) sod WT poe tT pheoso,t +6) Using the fae that» = (7/9), show tat "Note that te total ener, o inti proportional tothe square ofthe ample. Although we ave shown this proportionality ony forthe ease ofa vibvating sing, iis general reso and shows that he intensity of « wave is proportional othe square ofthe amplitude. If we had eared tverything through in complex wotton instead of sine and cosines, then we wovld have found that Pi proportional o[D, instead of ust DE. Generally there are many normal modes present the Sametime ad the complete solution is (Equation 2.25) 265.9 = 55 costs +4,)sn 2 ‘Using heft hte Polem 3-16) sin TE sin Ete =0 man show that ee ‘We begin with he potential enengy associated with the vibrating sting [rae sera] “{eGay fo Using the fet at (1 Staring withthe equation forthe mi normal mde yeasts +6, sn70 chara we obtain the pail derivatives ~a Dy sine + 4x mt cos 4,)cox T where, = ona /t Ths, SL Gye K, aD into, +0.) sit de [ wivisirto,e +o sit a SER fete +0 st de 2 pitts +4) ah Gs) Breton +4) [cot ax = TE prcottant +6) where T= pt. The al energy gvenby E.avtK, aint Teta? Dinas +6) + a Dicos(oys +6) = Dicosita,t +4) eppiias+ay+2 Lito. +9.) +eor%o,r +49] 100. = 3D, costes + 4)sin om To iad V and K, use the identity from Problem 3-16 [wt sin [oes Tai Wetton have Finally, “a 2 Yn Dieosw.t +4.) + DEsintlot +0) OS apace , 2S wi Di feoru,s +9.) +588 +90]3-92, The quantized energies ofa patce in a box result fom the boundary conditions, o rom the fact that the particle is esrited wa ite region. la chis problem, we investigate the quantum ‘mechanical problem ofa fee pac, one dat snot esticted wo a inte region. The potential nergy V(x) i equi o zero and the Schdinger equation is BY | me See MEvins0 — -w (2m Eh and Ba valed = fin eT ivenges. Therefore, & must be positive. Using Equation 3.11 forthe momentum operate, we find in (Ae Pike = RkA,e = bhy (0) For free pte, all energy is kinetic energy. The posible values ofthe momenta of fee parcleare hk and ~W. Using = p/2m, we ind that eh abt E £ am Finally, GLAD 09 = (Aer) Ae") = AA, =|A\l? = constant WEY, = (are) Ae) = AA, = [A]? < constant Since 9" (3) (a) isa constant, the price sequal key to be foun anywhere along the x axis, Thus, thre isan ifete uncer nthe locion of te parce. This consistent wih the UUncertsiny Principe because the momentum ofthe particle s known exactly (2, = 0). 3-33. Derive the equation forthe allowed eerie of pate in one-dimensional box by assuming that hepatic i described by standing de Broglie waves within the box. ‘The de Broglie relationship is aot a) 5 ) Because the waves are standing wave, an ntgrl numberof al- wavelengths wil nto the box, 2 Boao path = and oes ais nM Le 2B7 overs 3-24, We can use the Uncersity Principle fora particle in box to argue tht fee electrons cannot ‘eit in amicus. Before the discovery ofthe neutron one might have thot that mcleus of ‘stoic number Z and mass number A is made up of A protons and A — Z:elecons, hats, just, ‘enough electrons such tha the not nuclear charge is +Z. Such a nleus wou have an atomic ‘umber Z and mass number A. tn this problem, we wil we Equation 3.41 testimate the energy of anlectron confined to a region of nuclear size The diameter of atypical nucleus is approximately lor m. Subsite ‘ino Equation 3.41 and show tht, i 9, 23x kgm st Show thet pa Bests —x and so eoy-9 The Stoo Emon anda Paicina foe 75 Now show that (2) = f(x) Ge that Ais symmeti) fra patti box, and so show that AeOW(-2) = Bv(-8) ‘Thus we tcthaly,(-1) so an lgefuncton of belonging he sume genase Now, ieny one eigenfunction nace wih cach eigemale (ie Sate is ndegeners) tea argue that Ye) and -#) mst ifeoaly by muipicative constant fe tha (2) = cv, By applying the inversion operon ain hs ation show that ¢ = =1 and hat function most be eter even or 4 with espet to reftion tough he « = 0 line because the Hamiltonian operon symm, Thus, we ac tht he ymameny of the Hanon operator inflences te symmetry of e wave fnctions. A general sty of Syne uses group Her. fd this example i actully an elementary aplication of group theory to qv mechan woblems We wl sty group theory Chapter 12. Consider the wavefunetion found ia Problem 3-28, For od and the wavefunctions for even ae ansymmenic, We wil now show tht F(x) i an even function of [Now we have shown that E,9,(—x) = H(),(-1) = Hayy). Ite sae is nondegenerate, ¥e(-#) = e902) Repti he operation, we find YI = 08,02) = 2-9 “which leas to the conclusion that ¢— Land consequently othe conclusion tha all V2) ae titer even or od with respect to feection Uoagh the x = 0 ie. Thus the symmetry ofthe ‘iailtonian inflaences the symmety ofits egenfoncsons (assuming a nondegenerate syste).