lism in Quantum Mechanics 253 equation shows that y 1) does not depend upon Provided y is indeed a superposition of Oa (k) ‘0 ar a OY at lite $= the de-Broglie's idea, a wave'is to be aseos; 3 5 Associated with a moving particle. We shall have “th wave packets. A wave packet ean tn constructed by forming & group of plane waves We) = J ah doy sition of wave-functions for a free mv be associated wit a (10) Particle : Let a particle of mass m, moving with velocity th a wave of wavelength she mo ‘. B= Smt propagation constant k = eo tek = 2h 2 See ee Fat amt (11) we can be represented as srg (12) para exp 5 (m-£1). (13) ton of a'set of such waves, a wave packet can be constructed as shown in equation (5) wie) = Foi | apy ef PF EV ay, mA ir En 20) = Jaen J. Vee dk. (14) Joes not depend upon time, so 1 2 = (pwn) a) = Tent Ju. Yee DT de. (15) ula, ce i Hes J lyveo ok | a) |? dp = constant. TIVITY AND SIMULTANEOUS EIGEN FUNCTIONS Fiyo operators A and B possess a complete set of simultanous eigen vectors, then B commute, i.e.m Mechanics (With App Meat Quant (i. B=? an fA. oa an 8h Bho" basic vectors, then by or AB ete set Bey: j-th pen 2 PIES Fn qtion ofthese basic vectors, , i eer wees Pan Mog igen vectors OH a a Proof. Let ell Be theorem any wave fOAeUD ie a , 1 nace eae iil 1 of Aand 8 implies that where Cm (m= 2% jenn ot “The fact that eae On ne of 05152 em a bab , rs A a jn state Om respectively: rowan bas ooenlas of opera Now we have tyes sti = x Cm: AB bm = i Cm Abm om iz A 25cm bm (A Om) 7 “Fee ban n= 4n bm em Om ™ = Similarly, we have rs Bly =Bl Zen tn ose n= =2enb an re Senin on)= 3 nim m Om ” m -E Gnbntindm- Pe As mbm weno: ele BEL i and (5) are equal. Consequently dis oz (ABBA) y=0 ‘As choice of y is arbitrary, thecetor AB- AB=0 or(A, B= 0 i.e. the operators A and B commute if they have simultaneous eigen functions, ‘The converse of the theorem may be stated as follows : : Theorem. The eigen functions of comm ‘operators that they are simultaneous Sea ae can always be construc thus proving the thew? Or If If two operators commute, they possess a set of simultaneous eigen functions. Proof, Let A and and B be two given operators which commute with each other, i in such a ¥8)255 (1) 2) g A ABW) =a(B yy, that 8 : =) above equation sh ‘ teens fundamentally iY 8 an cigen function of A, belongi amentally diferent cans | belonging to same ei is non-degenerate (j : aan a Bema ‘S only one state y corresponding to eigen value a) ee : ¥ Independent eigen funeties with this eigen value. Cor IBY must be linearly dependeny, es : By=by igen cif nse~ VEC + Qyy that eqn. (4) is satisfied ie. -+.(6) ng this equation by wij and integrating over the entire Configuration space, we get +n ay CQ J wi By; areal yi BY2 dt =bC, fu Wi dt+bC J Vive dt ~ C1By + 2B =bC, +0. [where bu=[vibvi a ie C1 Bi~6)+CB=0 Jang Bra=|yi Byrd multiply (6) by w3 and integrate over configuration space, we get CyBa1 + Cp (Bor - 6) =0 -(7b) Bel By dcand a=] va Ba dt linear equations (7) determine constants C} and C). A non-trivial solution of equa- d the determinantQuantum Mechanics (With Applica, 256 By-b Bi2) _o, Bat By-b| (8 ‘The equation, quadratic in b, has two roots, say by and bo, for each of these roots constants sais, (7) can be found. If these roots are not the same, the eige! therefore linearly independent, so that the degeneracy have b operator B. If the roots of the determinantal equation are equal * i & 1 functions of B constructed in this way are othonormal ., een removed by means of the commu, qi I, then the function yy and Wo are als, simultaneous eigen functions of B. , This procedure can be generalised to cases having degree of degeneracy still higher but finite. 7p, equation corresponding to (8) for c-fold degenerate state is a” degree in b and has o-T00ts. If these all distinct, the degeneracy is completely, resolved. However ifthey are not distinct, then itmay be po sible to introduce a third operator C, which commutes with both A and B, by the help of C, the degeneracy is further resolved and so on. Ultimately we can expect to obtain a complete set of commuting operaio-, which determines a complete sets of orthonormal functions. It may be pointed out that in general the. will be many set of operators which will span the complete space. The discussion holds for Hermitig ‘operators only. The physical significance of these theorems is the following : The commutativity of operators expresses the possibility of measuring the corresponding physica quantities simultaneously or in other words the non-commutativity of operators makes a simul ‘measurement of corresponding quantities impossible. 7-21 THE PARITY OPERATOR The parity operator is a mathematical operator, denoted by ®t. For a function of variable x, it has: relation fy @ =v). Operating on wave-function yj and > with % operator, we get Riv @) +2 @))=Vi Cd +2 C0 = fy (2) +R @) And Rew (a)= cy x) = chy (x) for every function v Hence operator is a linear operator. : () %-Operator is Hermitian. The scalar product of my and 6 function is given by cy, elie: 2) 00) dx= Jv") (x) dv where «= Since the value of the integral is unaffected by renaming the variable of integration, w A aes: ey, eles (0) 6-2) de=(y, 20). The relation shows that 7 is also Hermitian operator. (ii) Eigen value of operator. The eigen value of operator fis given by relation : y= dy. Here 2 is eigen value of parity operator f in state y. Operating again by #, we obtain€ eigen function corn ions We and satisfy 2)] and (Ye) +y(— Hamiltoniay commutes with Hamil aN Operator is 943 1VQ)-yeay, n of a system, et tie Hamilton tonian is called the Constant of motion in Quantum 2 oe H: mt V(x). is operated on a function W(X), so that 2m age VO) + Vex) w(x) = Fle nak Vex) wea) ) = Baica, Vex) wx) because Ry(x) = w(x) and VQ) =Vi-a) = VQ) also = EH Han rd | =o at VO) WRx), [ae = Phy). (HH) w@)=0 w(x) #0, ig Hn-nA=(H,n)=0,Physical Applications of Schroedinger’s Equation to One and Three Dimensional Problems 5.1 THE FREE PARTICLE The Schroedinger wave equation for a particle of mass m, total energy E and potential energy V is written as 2m Vy + E-Yy=0 a t where’ =4, being Planck’s constant. A free particle is one for which potential energy V is quite independent of position and hence, for convenience, it may be set equal to zero, so that Schroedinger wave equation for a free particle becomes vay +23 By=0 nh @) or, in cartesian coordinates. 2 ah of Hy Sy, Fy, 2m yg @) Riga tat ee ara nv This is a partial differential equation in three independent variables x, y and z and may be solved by the method of separation of variables imposing the boundary condition that y is infinite everywhere in space since the particle is free to move anywhere in space, so that we may write the solution of equation (3) in the form w (x,y. 2) =X) YO) Z@), 4) Where X(x), ¥(y) and Z(2) are functions of their respective co-ordinate alone, Substituting this in equation (3) and dividing by X(x) ¥()) Z(2) we geta Quantum Mechanics (With Appice, tions) ‘The equation may be written In above equation L.H.S. is fu ant kz, (Say), $0 that, K Sie independent of x,y andz, ie., both sides must be equal to a co fraeXe | pa oe ole es, ae ey BIMDIAd re isto be satisfied both si eee, YP att Bay a wee! Yap ot Jue of 4,1 #Z_2m (11) may be written as Ist be caugey constant ky (say), so that equation R.H.S. is constant. Let this constant be k,, so that we may write ae / 5) 6) inction of x along, while R.H.S. is function of y and z and is indepeng, of x. Ibis, therefore, necessary that the value of the quantity to which each side is equal mus, fe e (1) (8) In above equation LHS. is ce ofz while R.HS. is independent of y. Therefore if above equation (10) (1) (12) (13) 2(l4) (3)ications of S inger’. ie al Applications of Schroedinger's Equation to One and Three Dimensional Probl roblems 143 ‘The general solution of above equation can be written as = VOmE,) Ma) = Ny sin“ DO xo} 9a where Ny and Xo are arbitrary constants. Similarly we may obtain the differential i, equation in yandz by _ substituting op? =i equation (10) and (12) respectively, viz., 2m aT Ey Y=0, ae 17) 2m and Epes) + (18) The general solutions of above equations may be written as VQmE, YQ) =Ny sin {Men 0 19) 3 VQmE, Z2=N, sn me ew. (20) Substituting values of ky, ky and k, in equation (19), we get E,+ Ey+E,=E. w(21), As any sine function is single valued, finite and continuous for real values of its argument, therefore for finite values of X, Y and Z, (i.e., y) Ey, Ey, E, and hence E must be positive. Thus the eigen (or wave or characteristic ) functions and energy values of the free particle are y=XYZ V(QQmE \. [NemeE) VQmE, =nsinf = (:-19} sin} qo O30) sin 2) (e- 20) 22) and E=Ex+EytE, - 23) where N= (Nx Ny N;) is a normalization constant, E,, Ey, and E; are positive. Clearly the free particle has continuous set of energy levels, however, the quantization may occur if the particle is not entirely free, but is constrained to remain in box, which we shall consider in the next section. The complete wave- functions with the time factor can be written as follows : “4 r, = \(QmE, ay SPS)» one pair 6g OME? 9-yoh in| 2) e-alle Eh ein V(2mE,) esa an of sn{ 9} xe Ete FEDYN Hsin OED oo} sin 6 raf snl -o} se: age 24) 52,.PARTICLE IN A BOX Let a single particle, e.g. a gas molecule of mass m, be confined within a rectangular potential box with edges parallel to the X\Y and Z-axes of lengths Jy, fy. and /, respectively. The Particle can move freely Within the region 0-a ; xfor0 E,= a (nt 7 20)Quantum Mechanics (With App, | “ation, re a1 welt the particle can have only certain : ears potential Wel values of a particle is caljeq :V@lucs It is clear that inside an infinitely deeP of energy cige 7 led itg «of coarar een quan o The ose nel) ae potential well is discrete, while 1. cnet spectrum. Thus the energy spectrum ig continu : y spectrum of a free particle without ‘boundaries, is con jes, x= Oandx=a and is calleg the boundari he ‘The least energy state has no ees Mods called frst excited state, the state core, £"Ung state. The state corresponding ton = Nding ; ited state and sO 0D- iB to n=2 has two nodes and is called second excite to condition of Normalization of veave-unction. According Mee normalisation, a wave function is normalised i A a(e)Pde=t ie Ixx| o {from (8)] or fan Deslaret [oo @) Bm 2 fa Be a [s-enoeses ie 2 Jo} n En Ma or zal ve x0 = ENERGY STATES oF so that A= a THE PARTICLEIN A WELL ‘Thus the normalised wave-function is given by Fig. 59. 2). (nt1)nx we Vlatene. “9 5.7 A PARTICLE IN THREE-DIMENSIONAL, INFINITELY DEEP POTENTIAL WELL. Let us now suppose that the particle is restricted to move in a box with sides a, b and c. Let the wal of the box be impenetrable and so the probability of finding the particle at the walls of the box is ie, V¥O.%»%)=WG0z2=yiry,0)=0 (A) G@y2=V¥ Gb 2=vay,c) -B) ‘The Schroedinger equation in three dimensions for a free particle constrained to move in the box is given by Hy Ay, Py am ( i in 0) ae a ag eee Lets solve this equation by the method of separation of variables, so that we may write , ; ¥G¥.9=Xa) . % Substituting this in equation (2) and dividing by ae ae ex ey az Xap *Vaat Batre 0. The equation may be written as xof Schroedinger's Ei 's Equatic ‘quation to One and Three Dime Pi 67 nensional Problems M 2. Yx2° 95377 & Fa ata is function of ‘ ‘a atte ae rx. It is, therefore, nec lone, while RWS, i yah at uno th se ma je is equal must each side must 8 lust be equal to a constant, ~ Ky stant, ~ ky (say) so that (6) i) regan we ‘4 2 equation L.H.S. is independent of z whil S. render refore if above 0 ‘ le R.H.S. is independent of : y. thet ‘to be satisfied, each ust be equal to a constant, ~y (Say), $0 that we have (8) equation may be written as Sy a Zee. ket ky 9) BaG+ 2 2.282 ane nee ef 10), solutions of (6), (8) and (9) are given 3° 1 sin byt + By 608 Ket Y= Ap sin kyy + Bo C08 ky)» Ze Ay sin kez + By 608 kets ‘boundary conditions (1A) to above equations, we get By = Br= 83 x= Aysin kee (A) All) YeAgsinky --(B) Za Aysinkgs ©)7 SSS "SS > Quantum Mechanics (With App Natio, ns) 168 fons we get ‘ ‘ to above dequations | Applying boundary conditions (1B) 10 Elian sin kyb=0> sin ke=9 . haat ani or Ee a ean 1 to zero ; otherwise y will be equal to zero ¢ n rt were ney and mare integers of which none is equal whole box, nS ie. ‘Substituting these value in (11), we get Ratiet XeAysin~ Z=Ay onl, Y=Apsin in equation (3) the wave functions are given by wend= at a Nate BAD i Asin sin Substituting these values ‘The normalised wave function is represented as 22 kynx . kymy Mee a in a BD (Wy V9) =TJFapq hg pin Substituting value of ky, ky, ky from (12) in oO te oe de Rates are expressed a a) emf Eqn= I Om | Clearly the value E=0 is impossible, For a spherically symmetric well, a= b=c; therefore the energy for such a well is | rer | Fasrynce sa etm +m).ons of Schroedinger's sof Schroedinger's Equation 1 One ang Three Dimensional Problems state energy for a spherically symmetrical well is z Fy, =e ma’ lear from (15) that there may be |= Bj12- The states giving the ante Several modes possessing the same energy nergy of a combination of quantum numbers forx<0 for0a e have a potential well of depth Vo between x= » (i) If a particle having energy E>0 es this well from the left according to classical ¢ of the particles turns back : but according ry the particles will be reflected from the es at x=Oand x =a, Consequently, there will and transmitted beams along with incident olye the problem, let us write three sr equations, one for each region. Fig. 5.10. ay 2m 7 +27 Ey =0. (3) F ar wv inger equation for II region is x SMe, 2 (E+ Vo) ya=0. --@) Bons dinger equation for III region is (4) nd yy are the functions for I, Il and IIl regions respectively. solutions of equations (2), (3) and (4) may be written as yi Ae ete a ine = inst yp = Ane + Bye" (6) ing = inal ys a Agel 4 Byer AD,176 - (51) yaaa 2p yea pi PE hh, The shape of curves 3 p2 for giver values of and p10? the same 814P! pe of curves tion of p2 FOF & a for each set of values ted aS il of aad Pls regent allowed valve of p2 fon the chosen Vall go a Rea rom fig, 5:12 eae there js but one all tis ol serete enerey levels yy and yp are also depends ‘The point chosen for py and & Ht nt. One E® rowed value of P2in every interval us rpersentine di > A, in this case, eqn. (12) becomes a oy @y=0. (13) og The solution of above equation is 2 weed? a (14) which may be verified by differentiating above equation twice with respect to q ; thus 2, 2 2 OV pts td 72 2 =@tnet? (is) As q is very large, q° +1 =” and so eqn. (15) becomes a 2 Seat tea,181 \ccording to this equation if qs «, he series governed by the Tecursion part making the wave function physically unacceptable. some restriction is introduced aie ee does not lead to a satisfactory wave function '¢ series break off after a finite number of terms. values of harmonic 2scillator _ From above discussion we have seen t, QO) must break off after a finite number of tor in the recursion for at in order to obtai terms. The series Tula (26) equal to zero, i, 2s42r+1—-220 = 2s _ For s=0, we have S+Qrt+ 1 in a satisfactory wave-function, the series will break off after rth term if we get the QI), Aare] » we have A=2re3 enerally as N=2n+15n=0, 1,2... tion (8B) we get ae =2n+1 ink Thus equation (31) may be writen more g (32) Substituting this value of 2 in equa a ( aa Jeane [since k= mas? from (3)) th (mos?) E=E,=(Qn+ yt Ex (nt ho (ns allowed integral values of n lead to certain discrete yalues of energy, Known as eigen values of the harmonic oscillator. Moreover equation (33) ls of harmonic oscillator are equally spaced, MORI had) 1 ACE) represented by equation indicates that the energy E=9/2ho is called zero point energy comparison with the result E = rih@p ob- -E,=3/2 ho shifted upward by an amount equal to ‘ er le Separation of energy levels, i.e. 50 zero point energy. Thus it is clear thatQuantum ‘Mechanics (With Applications) 192 ‘As function Yo (&, #) and wr ( #) are orthonormal yb (1) Yo) de=T Juimoyicnae Juraow (x, )dx=0 and =thotjho+0=no |ARMONIC OSCILLATOR consists of a particle bound to origin by a force having AZ anes respectively, ky kyandk, being the force tr along their respective directions, i.e. 5.10 THREE DIMENSIONAL H. armonic oscillator c* z along X, Yan ts of the displacemen F = ke ky kes ‘A. three-dimensional hi components — ket, — by and =k, constants and x, y, 2 the component where ky = ne mv 2 ky = 40 mvy (a) and ky = An mve he oscillation. Ye Yyand vs being respectively the frequencies of *. andz components of t Then the potential energy of the system is Lpetate ot gil 2 V athe + thy +9 he = 2m? mie? + vey + VE2)- so that Schroedinger equation, in this case, may be written as ay, ey, sy, 2m as aaa idle =0 ‘This equation can be resolved into three separate equati (3) ‘ons by the method of separation of variables Let us substitute y = X(x) YO) Z@) in equation (3) and divide by XYZ; then the Schroedinger equation becomes 12x 187192 LEX LAY LIZ, 2m pom (yex +vay + VE] = 0 + Xae Yar Za2 1x (2mm ¥) __ [a aty _(2nmyy P| [raz _( 2mmzy | _ Ime a) Xae ht Ya? fi FW Zagaalatt Bon, ‘ S. is a function of x only, while R.H.S. is a function of y and z and is independen’ ide is equal must be In this equation L.H. ofx. It is therefore, necessary that the value of the quantity to which each si independent of x, y and z (i-e., constant), so that PX _ ( 2nmvx ax n 5) 2m ee E, (say)ea, EaNation to One and Tp e vee Dimensional Problems 133 {yo (ry ~|122_ (2mm, 2i3-(me —2mE __ 2m, (6) ation (6) may be written ag 7 " oe FY _(2mmy, Za = =~ 1182 _(2mmvee 2mE | 2m ) | Zag | ee] | 2m 2m equation LHS. is a function of y only, S 5 ee $10 be satisfied, both sides my, while RLS. isa st be equal function of z only. Therefore if this I to a constant, ( _ 2m ‘ee WaeY | (eaatetay idy y i Ys a == 3h (8) 1 ez ‘. izes 2mE Zaz Jere any (9) uation (9) may be rewritten as 18Z_(2nm2 ece\n | = rks ttieeome 2m wie Fe (say) 18°Z_(2nmv,2 on a5 | Stites [a pare (10) 2m p 42m, _2mE_ Om Ga gear Ex+ By+E, = E, ay is (5), (8) and (10) may be rewritten as FX, 2m (Ex-2n?mvz 7) X = 0 (12) art 2 oY, 2g, anv? 9?) ¥ = 0 =13) ay # 2m (g,- amv? 2) z = 0 aay a? ow E,+.Ey+E, = E. (15) Above three equations is same as that of one-dimensional harmonic oscillator (see mn jon 2.9 with k = 4x” v5 m). ents of energy values are, therefore, given by,—=—— ties (With Appi eipaern cee Arc, ey a tee 194 (16) a= (net 2 eet Hence my myand ny are non-negative integers none osei sillator are given by ‘Then the energy or eigen values of three-timen imensional B = Bet Byte 5 epereaen te) a ‘The wave-functions are given by (18) (19) and ‘Thus the complete wave-function me yen = —— aed 4 P79 (ee ip (Gd) Hn, (4) Ha, 00) = In this case Ax, by and A are restricted tothe values A ote nye Sina 1 2 Ce a 4.