__, Quantum Chemitry GSIR-UGC-NET/JRF|GATE TIFR | BARC | ISe | DRDO | SLET | NTPC | ONGC-GT | HPCL | Ph.D Entrance First Edition : October 2014 Second Edition : September 2015 in collect he data and providing the solu jO8S. No peit ofthis book may be ropreducsd or lisher.PREFACE TO THE SECOND EDITION book “Quantum Chemistry” is written with the objective of providing description of principles involved in Quantum Chemistry in Physical Chemistry including their application at a level suitable for graduate and post-graduate students of Chemistry in different universities, This book will be highly usefial for the candidates preparing for various competitive examinations at national and state levels such as CSIR-UGC-NETURF, GATE, SLET, ete, © Inevery year CSIR-UGC-NET/IRF exam includes at least 24 to 28 marks from this section. » In every year GATE paper includes at least 4 to 6 marks from this section out of 100 marks, Apart from NET, GATE, PSUs this book will also be very usefizl to candidates appearing for various PhD entrance examinations. The book contains a brief description on important topic of Quantum Chemistry. Students preparing for competitive examinations are advised to go through every topic for their understanding and conceptual clarity and then get into solving the problems. For more practice students are also advised to go through our classroom assignments, Much care has been taken to minimize the typographical errors, yet if any noticed, then your suggestions are invited with a view fo improve the book in future editions. We would like to thank our respected faculty mesbers for their vatiable inputs in the book. Thanks to Mr. Neeraj Panwar, Mr. Surajit Paul aad Mr. Binay Dvrivedi for thei constructive support in doing corrections and proctiend Mohammad Firoz for formatting, designing and ng A vote of thanks ak bookSane csr CONTENTS SECTION-A. Chapter 1 : Basic Principle of Quantum Chemistry 01-25 Chapter 2 : Quantum Mechanical Concepts & Concepts of wave functions Chapter 3 : Operators Chapter 4 : Particle in Box Chapter 5 : Harmonic Oscillator Chapter 6 : Hydrogen atom & Rigid Roto Chapter 7 : Angular Momentum Chapter 8 : Tunnelling SECTION-B Chapter 09: Variation Principle Chapter 10: Perturbation SECTION-C Chapter 11: Molecular Orbital Theory Chapter 12: Valence Bond Theory Chapter 13: Hiickel Molecutar Orbital Theory SECTION-D Chapter 14: Atomic Structure 26-36 37-62 63-80 81-93 94-118 119-128 129-134 135-144 145-153 154-170 171-179 180-199 200-227Coc ae Care Chapter 1 COC nC ao Basic Principle of Quantum Chemistry Introduction (Philosophical View) Unlike Newton's mechanics, or Maxwelt’s electrodynamics, or Einstein’ relativity, quantum theory was not created or even definitively packaged and it retains to this day some of the scars of its exhilaranting but traumatic youth. There is no general consensus as to what its fundamental principles are, how it should be taught, or what it really “means”. Niels Bohr said, “If you are not confised by quantum physies then you haven't really understood it, Richard Feynman remarked, “think I'can safely say that nobody understands quantum mechanics.” Teaching quantum mechanics without the appropriate mathematical equipment is like asking the student to dig a foundation with a screwdriver. The first step in the development of a logically consistent theory of non-relativistic quantum mechanics is to devise a wave equation which can describe the covert, wave-Uke behaviour of a quantum particle. This equation is called the Schrodinger equation. The role of the Schrodinger equation in quantum mechanics is analogous to that of Newton’s Laws in classical mechanics, Both describe motion. Newton’s Second Law-is a differential equation which describes hiow a classical particle moves, whereas the Schrodinger ¢quation is a partial differential equation which describes how the wave function representing a quantum particle ebbs and flows. In addition, both were postulated and then tested by experiment. In classical physics, fundamental laws of physics are used to derive the wave equations which describe wave-like phenomena; for example, Maxwell’s laws of electromagnetism can be used to derive the classical wave equation which governs electromagnetic waves in the vacuum, In contrast, we shall view the equation governing the wave-like properties of a quantum particle as a fundamental equation which cannot be derived from underlying basic physical principles. We, like the inventors of quantum theory, can only guess the form of this wave equation and then test for consistency and agreement with experiment Www. Careerenceavour.com According to de-Brogl It was possible to associate waves with every moving particles in nature, This relation should hold also for heavier particles which we are able to see. But, on account of heavier mass, & becomes so small that there is a great difficulty in discovering the wave phenomenon associated with heavier particles This concept of the wave-particle duality of matter was subjected to experiment test by Davisson and Germer in |927 and independently by Thompson in 1928 who showed that a beam of electrons did indeed behave as if it were waves and underwent diffraction from a suitable grating, If electrons have the wave properties then there must be a wave equation and a wave function to describe the electron waves just as the waves of light, sound and strings are described. New Discoveries Prompted the Need for a better theory to describe the behaviour of matter at the atomic level. This better theory, called quantum mechanics, represented a completely new way of modeling nature, Quantum mechanics ultimately showed that it provides a better basis for describing, explaining, and predicting, behaviour at the atomic and molecular level. As with any theory in science, quantum mechanics is accepted by scientists because it works. (It is, quite frankly, one of the most successfully tested theories devised by science.) That is, it provides a theoretical background that makes predictions that agree with experiment, There may be certain conceptual difficulties at— first. A common question from a student is “Why is quantum mechanics this way?” The philosophy of quantum mechanics is left to the philosopher. Here, we want to see how quantum mechanics is defined and how to apply it to atomic and molecular systems. Quantum mechanics is based on several statements called postulates. These postulates are assumed, not proven. It may seem difficult to understand why an entire model of electrons, atoms, and molecules is based on assumptions, but the reasons is simply because the statements based on these assumptions lead to predictions about atoms and molecules that agree with our observations, Not just a few isolated observations over decades, millions of measurements on atoms and molecules have yielded data that agree with the conclusions based on the few postulates of quantum mechanics, With agreement between theory and experiment so abundant, the unproven postulates, are accepted and no longer questioned. In the following discussion of the fundamentals of quantum, mechanics, same of the statements may seem unusual or even contrary. However questionable they may seem at first, reatize that statements and equations based on these postulates agree with experiment and so constitute an appropriate model for the description of subatomic matter, especially electrons. iple of Quantum Chemistry Quantum mechanics is sometimes difficult first glance, partly, because some new ideas and some new ways of thinking about anatter:are-involved-Remember that the ultimate goal is to have 4 theory that proposes How-matter behaves, and that predicts events that agree with observation; that is, to have theory and: experiment agree. Otherwise, a different theory is necessary to understand the experiment, é The main ideas are: 5 The behaviour of electyons, by now kitown to have Wavelike properties can be described by a mathematical expression called a wavefunction, ° : within it all possible information that can be known about a system. thiéimatical-functions, but must satisfy certain simple conditions. For example, they mustbe,continuous. : The most important condition i that the wavefunction must satisly the time-dependent Schrodinger equation, With certain assumptions, time can bé Separated from the Wavefunction, and what remains is a time-independent Schradingér éqiationWe focus: mainly on the'time-independent Schrodinger equation. We focus mainly on the time-independent Schrodinger equation. In the application of these conditions to real systems, wavefunctions are found that do indeed yield information that agrees JAAD ira AGIESGR KEN Mole Quantum mechanics predits values that agree with experimentally determined measurements. To the extent that quantum mechaatics not only reproduces their success but also extends it, quantum mechanics is superior to their theories trying to describe the behaviour of subatomic particles. A proper understanding of quantum mechanics requires an understanding of the principles that it uses. On the basis of above discussion we may conclude that quantum mechanics properly, describes the behaviour of matter, as determined by observation.Basic Principle of Quantum Chemistry asd Uncertainty principle: Heisenberg’s uncertainty principle states that product ofthe uncertainty in determining the position and mo- A mentum of the particle is approximately equal to a number of the other , where oD / being Planck's constant, ie. Ap Ag=h () ‘where Ap is the uncertainty in determining the momentumand Aq isthe uncertainty in determining the position ofthe particle. According to above relation the smaller i the value of Aq , i.e. more, exactly we can determine the position, the larger is the value of Ap, ie. less excatly we can determine the momentum and vice-versa. The relation shows that itis impossible to determine simultaneously both the position and momentumof the particle accurately, Clearly this relation is fundamental since it sets a limit to the accurate and simultaneous measurements of position and momentum. The relation is universal and holds forall the canonically conjugate physical quantities lke position and momentum, eneryg and time, angular momentum and angle, etc, whose product has dimensions of action (joule-sec). Thus, if AE is the uncertainty in determining the energy of the’system and A is the uncertainty in determining the time to which this determination refers, then we must have AEAt=h (2) Similarly AJAO=h .G) where AJ isthe uncertainty in determining the angular momentumand A@ isthe uncertainty in determining the angle. The exact statement of uncertainty principle is The product of the uncertainties in determining the position and momentum of the particle 1 can never besmaller than the number of order >i. So, the equation (1) takes the form Ap Aq= ; h (4) Simileriy equation (2) and (3) take the form AEAt> $A LO hin * ‘And aaaetay c Dual Nature of Light and matter : Itis wellknown that light exhibits the phenomena of interference, diffraction, polarisation, photoelectric effect, Compton effect and discrete emission and absorption of radiation, The phenomena of interference, difftaction and polarisation can only be explained on the basis of wave theory oflight. These phenomena show that light possesses wave nature, on the other hand the phenomena of photoelectric effect, Compton effect and discrete emission and absorption of radiation can only be explained on the basis of quantum theory of light, according to the which light is propagated in small packets or bundles ofenergy fe or hv . These packetes are called photons or quanta and behave like corpuscles. Thus these latter phenomena indicate that light possesses corpuscular (or particle) nature. Thus we can say that light possesses dual nature. In some experiments it behaves as waves while in other experiments itbehaves as particles, IN 1923-24, de-Broglie proposed that the idea of dual nature (i. wave-particle duality) should be extended to all micro-particles, associating both wave and corpuscular characteristics with every particle. The experiments such as the those in which e/m of the material particles (electron, a -particle etc) is measured, indicate that the matter (i.e. material particles) possesses particle nature.Fy casernepeotavneumcnsntny Matter wave: Upto 1923 thematter was considered to be completely corpuscular in nature : but inthat year Louis de-Brogle proposed that a material particle such as an electron, protonetc. might have a dual nature, just asligh does. According to de-Brogiie a moving particle, whatever its nature, has wave properties associated witht. de- Broglie proposed that the wavelength associated with any moving particle of momentum p (mass mand velocity v)is given by CO pom where, his Planck’s constant. The wave assocaited with material particles are called the matter waves or de-Broglie waves, On the analogy of radiation the expression for the wavelenght 4, can be easily derived. he_h The momentum ofthe photon P= "= a Or, - (6) Simialy, the wavelength ofthe waves associated with material particle is given by act pm ‘The expression forthe wavelength ofthe matter waves, as de-Broglie did, can also be derived usingthe general equation ofa standing wave system and the principles of relativity, Other expressions for de-Broglie wavelength: The de-Broglic wavelength associated with a material particle of mass m and velocity Bs pom IPE, isthe kinetic energy of the material particle, then in non-relativistic (v<< Vs ° v> 1 : Variation of photo current Figure : Variation of photo current (i) with the intensity of radiation (1) (@ with Potential difference (V) |: //, t Von Vay ro. nm > Figure : Plot ofphotocumrent () agninst Potential difference V showing the variation of stopping Figure: PlotofE, agains potential (V,) with froqueney (j of radiation. @ There is a certain minimum frequency V, of incident radiation below which there is no emission of photo-electrons regardless of the intensity of the incident radiation. This frequency is known as threshold fiequency which depends on the material andthe nature of the emitting surface. Gi) The maximum velocity or kinetic energy ofthe emitted photoelectrons depends on the frequency of the incident light, not on ic’s intensity ie. blue light results in faster electrons than red light. The kinetic ‘energy of the ejected electron increases linearly with incident frequency. (ii) The emission of photo-electrons is instantaneous ie, no time interval between arrival of light at the ‘metai surface and emission of photo-electtons, no matter how feeble the incident light is. (iv) Ata fixed frequency, the number of ejected electrons increases with the intensity ofthe light but does not depend on its frequency. Failures of Classical E.M. theory: (9 According to wave theory, photo-electric emission should occur for any frequency of light, na concept of threshold frequency. 1 (i). According to wave theayys she eneray.efthe ineiflent lights distributed over the entire wave front. So, electrons will take some tinie to eject from thie Surface 1, no‘ concept of instantaneous emission. & (iii) The electric field and magnetic field of the incident light wave exert forces to liberate electrons from the metal surface. So, the light of higher intensity consists of stronger fieids and should give higher velocity to the photoelectrons, Einstein’s hypothesis: 6) The etuission and absorption of radiation takes place in descrete quanta of energy ¢ = hv Gi) Energy in light is not spread out over the entire waveftont but is concentrated in small packets known as ‘photons’. The incident photon on the metal surface can transfer the whole energy to one electron without any time lag, 2. (iii) A certain minimum energy called the work function M, is required (o release an electron from the metal surface, SsSoln. Soin. Photo-electric equation: When a radiation of frequency v is incident on the metal surface in vaccum, it can be either be reflected from the metal surface or it can be completely absorbed by an electron, In the second case, the electron can be knocked out of the surface. The emission of electron fromthe metal surface is possible only if hv > Wy. The remaining energy (hv ~W,) canbe utilized to impart kinetic energy of the emitted e!eeteons. Frou hoW, Eghy [PLP"| Figure : Mechanism of Photolecttic effect. So, the maximum kinetic energy of the emitted electrons, 1 Fu =e =hy -Wy= hv —hyy where ‘m’ isthe rest mass ofthe electron, v,,, is the maximum velocity ofthe emitted electrons and v, isthe threshold frequency. This s the well-known Binstein’s photo-electric equation, Explaination of Photaclectric effect: (i) If v 2dx-=144 => d=14d3 Soln, Sota. Soin. Basic Principle of Quantum Chemistry ‘Calculate the wavelength of thermal neutron at 27°C 7 Seen 71 2x16 x10 «1.3810 x 300 he ‘Show that the de-Broglie wavelength } associated with moving electron isthe 2 h 6.610 12.28 5 he OT Bmxelv J2x9.1xi0" «16x10 Vy Ww Heisenberg uncertainty Principle: A A h h h A AxAp,2>=; AxAp, 2—~; AE At>~; AB Ar>-—; AV AGE—; AJ AG2>— 5253 Avy, 2 a5 3 Tage edetn Sema aerae Al isthe uncertainty angular movement 4@ is the uncertainty in the cotresponding angle. Anaclectton asa sped of 50 msec withan accuracy oF 0.005%, Calelate the uncertainty with wich we can locate the position of electron. h h — = Arxmy = 4n 4a. 6 Sed Army 4x3.14%9.1x107 50% 0.005 The average time that an atom retains before re-emiting in the form of electromagnetic radiation is 10* second. Calculate the limit ofaccuracy of excitation energy. h Ag At= 4a 7 6.610% 26 SAx10 , = =0.54%10 Joule = 9 joule = 3x10 eF $3140" OT eR EE Ifa component ofa angular momentum of the electron in Hiatomyis known to be 2f with5% energy, the angular orbitals in the terms of angle Since, we know that, Ax Ap, 23x10%m (+ b=6.6x10™) 8 Soln. sore Ag=s° Calculate the de-Broglie wavelength ofanelectron having a kinetic energy of 1000eV. Compare the result with the wavelength of x-rays having the same energy. The kinetic energy, = 10002" =1.6x1 0S 2m /6.626% 10™ js [2x(9.tts10 kg) (160%s)"] = 0.39% 10 nt = 0.394 act P R _ he or x-rays, energy =F (6.626x10" Js)x(3x10° m/s) 2.42 x10 1.42.4 16x10 wavelength of x-t 424 ys av =31.85 de-Broglie wavelength of electron 0.394 9. What is the de-Broglie wavelength ofan electron that has been accelerated through a potential difference of 100V? . ITIFR 2014] (a)0.123nm ——_(b) 0.123A (0) 1.2310" em (d) none of the above Soln. ‘The energy gained by he electron= 100 eV. Then, P 2m =100eV =(100 eV’)(1.6x10"" Fier) p=[2(9.1x10"Ag)(1.6x10"J) | 396 x10 kg ms a= t=200 eV =3.2%\0"F = 1.23%10m=1,134 = 0.123 nm Pp Correct answer is (a) 10. Determine the de-Broglie wavelength ofan electron that has been accelerated through a potential difference of 200 V. Soln. ‘The energy gained by the electron = 200 eV. Then, P 2 200eV =3.2x10J 2m 7 : wy Wee ‘ p=[2(2.b<10° fe) (32 x10 4] = 7.63210 kgms”! A _ 6.826410 Is 9.368510" m = 0.8684 p 1.632x10™kg ms Il. Estimate the velocity of neutrons needed for the study of neutron difftaction of crystal structuresif the inter- atomic spacing in the crystal is ofthe order of 2A. Also estimate the kinetic energy of the neutrons correspond- ing to this velocity. Mass of neutron = 1.6749%10 kg. Soln. de-Broglie wavelength Az 2x10 m h or y= A = mv ma = 6.626x 10s. = *"[heva9x107 g)(2x10" m/ 1OTB«I0' msBasic Principle of Quantum Chemistry 12, Soln. 13. Soln. M4, Soln. 15 Soln, Kinetic entry, T= J? = (1.6749%104g) (1978.10 ms") =3.2765x 107! J = 20.478x10" eV What is the ratio of the kinetic energy ofan electron to that ofa proton if their de-Broglie wavelength are kinetic energy of electron Kinetic energy of proton Anelectron has a speed of 500 r/s with'an accuracy of 0. locate the position of the electron, Momentum p=mw =(9,11*10kg) P1090 = 0.004 P A ‘Ap 1822%10 0.004 (9.135107'4g}(500:m/s) 1m, =mass of proton T1836 mh ate the certainty with which we can x (500 ms) kgs ‘The position of electron cannot be measuired to accuracy less than 0,036m, ‘The average lifetime of an excited atomic state is 10s. Ifthe spectral line associated with the decay of this state js 600A, estimate the width of the lihe. A105, A= o0siok COMIOGTENDeAVOUr.COM daz 36x10 m? AmcAt 4x (3x10° m/s)x(10?s) Anelectron in the n=? state hydrogen remains there on the average of about 10° s, before makin a transition ton= | state (i) estimate the uncertainty in the energy ofthe n=2 state i) what fraction of the transition energy is this? (Gil) whats the wavelength and width ofthis line in the spectrum of hydrogen atom? (page A, 6626x107 4a Axx10°s (i) Energy of n= 2» n =) transition =9.5x104m 13.6 €V0.52710°°J =3,29x10 eV Io 1 Sc lf Se Iga 16. Soln. Soln. 19, 10.2 eV (11 =-13.6 eV | PT AE _3.29x10% eV 7 =3.23x10" Fraction“ -—“T99 ey ic _(6.626x10™ Js} «(3% 10" mis) = 1.218107 m= 122 am (10.2x1.6x10"°J) Gi) 4= AE _AA Ea Ad =(3.23%10")(1.218%107 mm) =3.93% 10m =3.93%107 nm or Ad~ Ex E Ifthe positionofa 5k eV electron is located within 2A, what is the percentage uncertainty in itsmomentum? Ax=2x10°°m; ApAx= e 4a hn _ (6.626x10"*Js) mx &x(2x10™m) dpe = 2.635x10"* kg ms! V2imE = (2%9.11%107" x5000%1.6%10")""= 3.81810 kg mo 5x10 Percentage of uncertainty = 4? 5100 = 2 100 = 0.69 Sf 818 x: ‘The uncertainty in the velocity of particle is equalto its velocity if Ap.Ax location is its de-Broglie wavelength. Given Av=v-Then, , show that the uncertainty in its Ap=mAv=my= p Axx dy or P Mily CATE AYO GOI ‘The work fiction of barium and tungsten are 2.5 Vand 4.2 eV, respectively. Check whether these material are usefil ina photocell, which is to be used to detect visible light. The wavelength 4. of visible lightis in the range 4000-7000 A. Then, he __(6.626%10™ Js)(3x10* mis) % — (4000%10"m)(1.6%10"? JieV) Energy of 40004 light = 3.106 eV 6.626 «10™ aCe 7000x10-" x1.6x10°" ‘The work function of tungsten is 4.2 eV, which is more than the energy range of visible light. Hence, barium is the only material useful for the purpose. Energy of 700A light = Light of wavelength 2000A falis ona metalic surfac, Ifthe work function ofthe surface is 4.2 eV, what is the kinetic energy ofthe fastest photoelectric emitted? Also calculate the stopping potential and threshold wave- length for the metalBasic Principle of Quantum Chemiatsy. Soin. ‘The energy ofthe radiation having wavelengtts 2000A is obtained as hie (6.626%10 Js}(3108 mis) A (2000x107 m}{1.6x10- SreV) Work function=4.2 eV KE of fastest electron = 6.212-4.2= 2.012 eV ‘Stopping patential= 2.012 V = 621200 he work function Threshold wavelength 4p = (6.62610 Js)(3«10" m/s) ee DF (47510 m)(1.6x10°" J/eV) Stopping potential =2.62-2.14=0.48 V 20, Anelectronaccelerated through & potentiat difference of y volts impinges on anickel surface, whose (100) planes have a spacing d=351.5x10m(35).5 pm). The de-Broglie wavelength of the electron is Wa 3 a_fa Stee (3 . The value of a”involts is 2 [GATE 2008] pm \e - (a) 15x10 (b) 1.510% (0).6.63«0% (@)2.5x10" Sol, Given, + ey : a ofn, —=/— g fa. Given TS ) 6.6x10™ (a)* Sox 9.1610 o(pm} (9) 6.610 351.5x10 m=351 ‘mm v2 —=(a > 29.1220 (pm) ) [ene (66x10) (6.6x10™) 43.56x10% 29.1210 x( pm)! a=tsxi0® Correct option is (b) IpBasic Principle of Quantum Chemistry 2. Soln. If Ay and AP, are the uncertainties in the y-coordinate and the y component of the momentum of particle h respectively, then, according to uncertainty principle AyAP, is: ( Pe ao ) J (en (by >A/2 (>A (@2h/2 — [GATE2012] Since, we know that, h Uncertainty principle, A Ap, > Correct option is (4) www.careerendeavour.corBasic Principle of Quantum Chemistry Concept of Wavefunction Quantum mechanics acknowledges the wave-particle duality ofmatter and the existence of quantizationby supposing that, rather than travelling along a definite path, a particle is distributed through space like a wave. ‘The mathematical representation of the Wave that in quantum mechanics replaces the classical concept of trajectory is called a wavefunction, (y) (psi), The Schrodinger equation is a second-order differential equa- tion used to calculate the wavefunction of system, The Schrodinger equation: For one-cimensional systems. Bd EY yok Sgt ey =Bv where /(x) isthe potential energy of the particle and E is its total energy. For three-dimensional systems. # 2m oy tye Ey where V may depend on position and y? (del square) is ast Oy ae Inthe general case the Schrodinger equation is written where #7 is the hamittonian operator for the system: yar ae 2m Forthe evolution ofa system with time, jt isecessary to solve the time-dependent Schrodinger equation: allthe dynamical information about the system it describes. Here we concentrate on the information it caries about the location ofthe particle. ‘The interpretation ofthe wavefunction in terms of the location of the particle is based ona suggestion made by Max Born. He made use of an analogy with the wave theory of light, in which the square of the amplitude of an electromagnetigavave'ina regionjs interpreted asitsintensityand therefore (in quantum ers} Sa measure of the probability of finding a photon présent in the region. The Born interpretation of the \wavefimction focuses on the square of the wavefunction, Ifthe wavefunction ofa particle has the value y (xc) at some point x, then the probability of finding the pavticle between x and (x + dx) is proportional to |y,[' dx ‘Thus, |y,|'istheprobabilty density, and to obtain the probability it must be multiplied by the length of the infinitesimal region dx. The wavefunction w (x) itselfis called the probability amplitude. Fora particle free to move in three dimensions (for example, an electron near a nucleus in an atom), the wavefunction depends on the point ‘r* with coordinates x, y and, and the interpretation of y (r) iss follows then the probability of finding the particte in Ifthe wavefunction of'a particle has the value Yat some point‘ an infinitesimal volume dr = dxdydz at that points proportionalto |y[’ dtof e Basic Principle of Quantum Chemistry @ ‘The square ofa wavefunction isa probability density, and (in three dimensions) has the dimensionsof length’. It becomes a (unitless) probability when multiplied by a volume: In general, we have to take the account the variation ofthe amplitude ofthe wavefunction over the volume of interest, but here weare suppos- ing that the volume is so small that the variation of y inthe region can be ignored, Mathematical feature of the Schrodinger equation is that, ify’ isa solution, then so is Ny , where N iS any constant. This freedom to vary the wavefunction bya constant factor means that itis alwayspossible to find a normalization constant, N, such that the proportionality of the Bor interpretation becomes an equality. We find the normalization constant by noting that, fora normalized wavefunction Ny the probability ‘that a particle is in the region dx is equal to (Ny )( Ny )ax (weare taking N to be real). Furthermore, the sum overall space of these individual probabilities must be 1 The integration is overall the space accessible tc the particle. For systems with spherical symmety it isbest to work in spherical polar coordinates,0 and g. x=rsindcosd, y 1, the radius, ranges from 00 oo @, thecolatitude, ranges from 0to the azimuth, ranges eam 0t0 2 Standard manipulation then yield. de =r sinOdrdodg Interpretation of the y functions: | ‘The eigenfunction y is by nature a sort of amplitude function. In the case ofa light wave, the intensity ofthe light or energy ofthe electromagnetic field at any point is proportional to the square ofthe amplitude of the wave at tat point, From the point of view of the photon picture, the more intense the light atany place, the more photons are falling on that place. This fact can be expressed in another way by saying thatthe greater is the probability ofa photon being witbin that region. tis this interpretation that is most usefull when applied to the eigenfunctions of Schrodinget’s equation. ‘They are therefore sometimes called probability amplitude functions. If y (x) isa solution of the wave ‘equation for an electron, then the probability of finding the election within the range fromyto x + dis given bylyf de ‘The physical inerestatinof te sorfrtonas 4 probably amplitude finctionbreeted inst Via! Care VOU i ‘mathematical conditions thit'it mt’ obey Tt Sy i eith ty ‘Sash --valued, finite, and continuous for allphysically possible values of x must have one and only one value. It cannot be infinite at ay paint, for then the electron would be fixed at exactly that point, which would be inconsistent with the wave properties. The requirement ofcontinuity is helpful in he selection of physically reasonable solutions for the wave equation. Since the function y maybe a complex quantity the probability is written more generally as y*y where y* isthe complex conjugate of y . Thus, eg,,ify =e", y*=e" The probabilstics nature of quantum mechanics disturbed many physicists, including Einstein, Schrodinger and de-Brogli, (Einstein wrote in 1926: “Quantum mechanics says @ lot, but does not really bring usany closer to the secret ofthe Old One. I, at any ale, am convinced that he does not throw dice,” When someone pointed. out to Einstein that Einstein himself had introduced probability ito quantum theory when he interpreteda light wave’s intensity in each small region of space as being proportional to the probability of finding aphotonin that region, Einstein eplied, * A good joke should not repeated to0 often”. These scientists believed that quantum mechanics does not furnish a complete description of physical realty. However, attempts to replace quantum mechanics by an underlying deterministics theory have failed. There appears to bea fundamental randomness innature at the microscopic levelBagic Principle of Quantum Chemistry “The Born interpretation puts several restrictions on the acceptability of wavefunctions. The principal constraint is that y- must not be infinite anywhere, (in other words, y' would not be square-integrable) the normalization constant would be zero, The normalized fiction would then be zero everywhere, except where itis infinite, which would be unacceptable. The requirement that y isfinite everywhere rules out many possible solutions of the Schrodinger equation, because many mathematically acceptable sofutions rise to infnity and are therefore physically unacceptable. The requirement that y is finite everywhere is not the only restriction implied by the Born interpreta- tion. A solution of the Schrodinger equation tat gives rise to more than one value of function at asingle point is not accetable. ‘The Born interpretation implies that such solutions are unacceptable, because it would be absurd to have more than one probability that a particle is atthe same point. This restriction is expressed ty saying that the wavefunction must be single-valued; that have only one value at each point of space ‘The Schrodinger equation itself also implies some mathematica restrictions on the type of functions that will oceur. Because it s a second-order differential equation, the second derivative of y_ must be well- defined ifthe equation sto be applicable everywhere. We can take the second derivative ofa function only if itiscontinuous, At this stage we see that y_ must be + Continuous + Have a continuous slope + Bea single-valued + Should be finite. A patticle may posses only certain energies, for otherwise i wavefunction would be physically tunaocetable. That is s 2 consequence of the restriction on its Neeanbtn the energy of particle is quan- = aveere ‘The wavefunction must satisfy stringent sbhoe for itto be acceptable. (a) Unacceptable because it is not continuous, at x (b) Unacceptable because sso ¢ is disco arte Balad, 5) (©) Unacceptable because rN eee ad UICC OUE (@ Unacceptable because itis infinite atx=0 ‘We have claimed that a wavefunction contains all the information it is possible to obtain about the dynamical properties of the particle (for example, its location and momentum). We have seen that the Born interpretation tells us much as we can know about location, but how do we find any additional dynamical information.“MATHEMATICS INVOLVED IN QUANTUM CHEMISTRY” 1. Useful Differentiation: ae OR a = @ Ssinx= cosx qd. a (6) ,Sinar =cosar- Sar = acosax a MQ GIOLOMSOZLOMIOGIA ® 270-10. Siro 9 Eres) 2. Useful integration: a (wy fre on (y fetde=e" (3 fear @ [2ar=inx (9) [sinxdx =-cosx (6) Jsinaxdr=- 8S (7 Jowsse sits (8) Joosarax=2 x -sin2bx 2. (9) [ sin? bxdx cos 2bx “ab (10)fxsint ds = = Esme E x, sin2bx in(a=b)x (11) feos bd = =D (12) Jsinaxsin bud *"3(a=b) (arb) eof 1 (13) pf sin’ bid = = ) sina scosas (14) sinaxcosbx=—4 WA Integration of multiplication of two function u= ule), v= v(a)s Jind Jo is SUC (1-cos 26x fsin? oxd =Ih 3 dx fear Jreos2bxa aly 292 2 ‘ll Jsindcosbde = [2] _! 2 2b 4b Joos bxte=[(4 : de 1 fax ‘ 5 Joos2bxde=3 ‘Basic Principle of Quantum Chemistry Bat Properties of Logarithms: ()) lnm" =n lnm Q) tn = Inm—Inn Qin (mxn) ||“ )1 Jo jo 2 |v} 2 | ai|araltna| cos}==}—-)— [0 j-1 ja a |a}z | | JPsin x dx =—[eosx [i cosx dc =[sinxf = sin sin =1 Trigonometry: 2 _tre082x 2, _ [+008 2x (sin x= —— (2) cos! x= SEE (3) sinxcosx ae iat ae 14-005 2ax. : —_ (6) sinaxcosax = (5) cast ax = mile Some useful integrals: ) fxtetae=(x"e™ Ja)—(n 1a) [x™eMde @ [pea =(nv gh lh wtaartbrendeseourcom oo at, _ og? @ [re ae= Sala (a [pre ae eat les sar gy | olive de=—Nala (freer ae aa (2n-1) [ox 0 Ber) mG 2m = (10) fe“ér=(1/a)(I-e*) sin2x , cos2x 4 8 xsin2x _c0s2x 4 8 2 dee dx = 7+ (12) | r00s? xdx =“try Basic Principle of Quantum Chemistry Matrices: ‘A collection of numbers arranged in p rows and q columns is called a matrix of order (pq), reads as p by aquimairx, Bach number is called ‘element ofthe matrix’ ‘An element ina matic is located by specifying first its row and then its column, For example, ifa matrix [A] is defined as. a, a a, ay a yy 4, [= hy dy 4, 4, Bp Ap Oy 4 then , ison ofits clement which ocours inthe? row and j* column, ‘The elements can be pure or algebraic numbers, real or complex. A matrix having a complex number wil have conjugate matrix for example, 12 wees fly 2 [= 4. {| 'sconjugate | Ae | ‘A matrix can be rectangular (pq) or square (pp or q*q), or one contaning a single row (1*q) or @ single column (pX!). A ow of cotumn matrix is called a ‘vector’. Determinant of a matrix: 2 [4l- ; if then Det. =|4 { An (xa)-(»2)-6 Te 2S fies The determinants otis afam | 4 | are same and equal to ~2 though the matrices are different. Diagonal Matrix: AA square matrix is sai to be diagonal ifal ts off-diagonal elements are zero, 100 0 2 WIA races Forexanple, VS onal nate a Transpose of Matrix [A The matrix obtained by interchanging rows and columns in (Al is called transpose [ A] of matrix [A] 12) pais For example’ ld-[} ql oxa[A]-|, 4| Inverse of a Matrix [A]. ‘The inverse [ AY of the matrix [A] is defined by the relation (all L404) 3) in an n- dimensional abstract space or vector space, A=(4,,4,...54,)- On the other hand, such veetors have profound use in quantum mechanics. Algebra of Vectors: Addition: if A=(4,, 4,4.) and B=(B,.B,»B,), then As B=[(4,£B,),(4,28,) (42 The two vectors 4 and B will beequalif 4, =B,, 4, =B, and A, =B, The addition of two vectors may be represented geometrically in three dimensional space as follows. Let 4 and § be represented by two arrows. Bring the head of B to touch the tail of 4 without changing the direction of the either, then draw another vector @ from the tail of B to the head of 4, the resultant +B. Q Zn R Multiplication: There are two types of tlipcaton ia vector algebra ‘salar’ “do multiplication and ‘vector’ or ‘eoss" multiplication, Scalar product of two vectors is defined as, A.B =|A\|Blcosd 0) The i ciea whete, |A| and |B] are the magntidues of the vectors and @ is the angle between the two, all three being scalar quantities, the dot product is Scala If 6 =90°, the product is zero and in that case the vectors will be called ‘orthogonal’, “The unit veotors 7,7 and if along the cartesian axes ate orthogonal, ie., {£9 =0, we have ‘non PO FECTENC GE ii=l, jj =land k. =l vera a ‘The product of two vectors 4.B may be written analytically as ber, AB=(ai+4,7+48)(Bi+B,]+ 8.) oi) Because in view ofthe ‘orthonormally’ ofthe unit vectors, six of the nine terms inthe dot produt are zero. db - a The product of A with itself (@ = 0) is 4d =|A\]Afeos0 =|) |Alis the ‘norm’ ofthe vector A ‘The scalar product applies to vectors of any dimension, for example, for n-dimensional vectors, AB = AB,+A4,B, +... 4B, il)Basic witere, A's and Bs (I= 1,2, 09 0) are the components of the vectors in the vector space. For three dimensional vectors, there is another type of produet, the vector or cross product, defined as Ax B =|A\|B|sinoi swhiere, j isthe unit vector which makes the cross product also a vector, The product veetor has the direction ‘perpendicular to the plane defined by 4 and & such that the three vectors 4,8 and Ax B forma right- handed screw system rotating from A to 8, It follows that Ax B=-Bxd and dx A=O. The unit vectors are related as J ‘The cross-product can also be written analytically as, AxB=(4i+4,i+AK)x(Bi+B,7+B4) =(4,B,-4B,)i +(4,B,~ A,B.) 3 +(4,B, -4,B:) which can also expressed as a determinant 22, PGR AG A, Al lA, 4) JA, 4 eA AU ala al" |B, B,| B, B, B, ° Soin. Vector Representation of wave function: Schrodinger equation for a One dimensional system leads to an infinite set of orthonormal wave functions defined by fu. Gv. (s)de=5,, 0) where, 5,,, <1 for m= n (normalised) and 0 for m #n (orthogonal). The terms orthogonality, normalisation and orthonormality are adapted ftom the language of vector analysis. A set of M vectos X,, X,, is orthonormal ifthe scalarpinddutt, 73 ra (¥,,¥,) =6,(=1 for i= j and 0 fori j) Orthonomal vectors, like orthonormal wave functions, are lincarly independent, that is, they form coordinate basis for the vector space. Any vector can be expressed asa linear combination of the orthonormal set of vectors. X=3a8, .G) where, d's are the coeficients of te linear combination (scalar quantities) and é,, is the unit vector. (In 3- dimensions, X = aj +a, +a,k ). The coefficients can be obtained from the relation a, =(2,-¥) (4) Compare with a wave function ¢ as linear combination of orthonormal set of Wave functionsBasic Principle of Quantum Chemistry 22. Soln, 9= Lave -) where, 4, = fund dr 6) The analogy is complete if the wave functions y,, and y, in equation (1) are made to correspond to the vectors X, and X, respectively that is, by definition, is given by (4.-4,) 2A4.(@)-4,(@) ~@ where, the 4, (a) and 4, (a) are the components of the vectors 4, and A, respectively in the direction a and N isthe dimension of the vector space (For V =3, a =x, y and 2). For orthonormal vectors, (4u-A,)=8.u =l for = 1 = 0.for men ‘Suppose y, and y,, are two hybrid orbitals IGATE 2014] Y, = 0.124, 40.635), +0.77Y%5,, Vi, = 0.12, -0.63y,,, “0.7155, ‘What is the angle between them is viv =Willvaleose \vil= y(0.12)7 +(0.63)° + (0.7)° va|=toa2 lol = (0.12)? +(-0.63)° + (0.72) [val =1.0082 cosg = Viva Walls] cos 6 = -0.3969 + 0.944 AYS929 FE cos 6 =~0.9754 @ = cos" (~0.9754) =178° YOULCOM6. 10. U. Basic Principle of Quantum Chemistry Suppose y, andy, are two hybrid orbitals =0.1ly,,+0.82y;,,, +0.59Y2,, Yh, = 92, — 8-28 2p, 0-5, ‘What is the angle between them, How much energy is sequired ta remove an electron from the n=8 state of a hydrogen atom? Determine the maximum wavelength that hydrogen in its hydrogen inits ground state can absorb. What would be thenext smallest wavelength that would work? State the equation for the energy ofthe nth state ofthe electron inthe hydrogen atom and expressit in electron volts. Construct the energy-leve! diggramt for doubly ionized lithium. What are the potential and kinetic energies ofthe electron inthe ground state ofthe hydrogen atom? ‘A microscoper using suitable photons is employed to located an electron in an electron in an atom within a distance of0.1A. What is uncertainty involved in the measurement of its velocity? Mass ofelectron=9.1*10- kg and plank’s constant (h) = 6.626*10™ Js, Acricket ball weighing 100g is to be located within 0.1. What is the uncertainty in its velocity? Evaluate the ratio of the de-Broglie wavelength of electron to that of proton when (i) both have thesame kinetic energy, and (i) the electron kinetic energy is 1000 eV and the proton KE is 100eV Estimate the energy of electrons needed for the ‘study of electron diffraction of crystal structures ifthe inter- atomic spacing in the crystal js of the order of 2A. A subatomic paticte produced ina nuclear collision is found to have a mass such that Mc’= 1228 MeV, with anuncertainty of +56 MeV’. Estimate the lifetime of this state. Assuming that, whne the particle is produced in the collision, it travels with a speed of 108 m/s, how far can it travel before it disintegrates? The wavelength corr ron top enn (@) 44m Gd AK, x-ray emitted by one hydrogen atom strikes a second hydrogen atom and undergoes photoelectric absorption with an L shell electron. What energy does the ejected electron have? (@) 13.60V (b)34eV (©) 10.2eV () 68eV Inthe photoelectric effect, the threshold wavelength is 2756A. Iflight of wavelength 1700A is incident ona metal substance, determine the kinetic energy of the photoelectrons, "e / (a) 4.50eV ()2.25 eV (c)3.60eV (a) 2.79 eV Aso 5 rnsien ntisioms Mauer COVOUE GS om Bae 15. 16. 17. 18.Basic Principle of Quantum Chemistry = iq 15. 18 A retarted potential of 2.38 volt just suffices to stop photoelectrons emmitted from potassium by ight of frequency 1.13*10-s". The work function for potassium is (a)2.29eV (b) 4.67 eV ()7.05eV (@None ofthese A He" is accelerated from rest through a voltage drop of 1.000 kelovolts. The final de-Brogtie length is (a) 0.22PM (b) 0.28 PM (€)3.2PM (@28PM Asperthe uncertainty principle, Ax-Ap, = [GATE 2001] @h () hin Oa (@) zero The de-Broglie wavelength for a He atom travelling at 1000 ms“ (typical speed at room temperature) is (99.710 m — (0) 199.4x10 m_ (©) 199.4x10"*m (4) 99x 10% m [GATE 2009] ANSWER KEY ‘Questions z 3 4 6 7 Option D2ieV wanm | B56, | 136eV | Au=06D107 ms" ‘Questions a 9 10 a @ Option | au, =0szixi ms" | (42.85, | 3765eV | S86x10% mw (a) : (i) 13.55 {Questions 3B m4 is 16 a Option @) (@) (a) a) @)oon or Chapter 2 CoC oC oo Quantum mechanical concepts & Concepts of wavefunctions Quantum Mechanical Postulates Postulate 1: ‘The state ofa quantum mechanical system is completely specified by a flunction y (7,1) that depends on the coordinates of the particle(s) and on time. This function, called the wave function or state funetion, has the important property that y"(F,/)y(F,t) dr is the probability that the particle lies in the volume element dr located at 7 at time ¢ ‘The wave finction must satisfy certain mathematical conditiots because of this probabilistic interpretation, For the case ofa single particle, the probability of finding it somewhere is 1, so that we have the normalization condition Jv (dy (Fade =t It is customaty to also normalize many-particle wave functions to |: The wave function must algo be single- valued, continuous, and finite.” Pastwtate 2. To every observable in classical mechanics there corresponds a linear, Hermitian operator in quantummechanics. Postulate 3. -Inany measurement of the observable associated with operator A , the only values that will ever be observed are the eigenvaluesa,, which satisfy the eigenvalue equation Ay =ay This postulate captures the central point of quantum mechanis,the values of dynamical variables canbe quantized (although itisstil possible to havea continuum of eigenvalues in the case of unbound states), Ifthe systemis in aneigenstate of A with eigenvalue a, then any measurement of the quantity 4 will yield a. Anarbitrary state can be expanded in the complete set of eigenvectors of Le, y-3e In this case we only know that the measurement of 4 will yeld one of the values, but we don’tknow which one. ay, as However, we do know the probability that eigenvalue a, will occurs fo|° Animportant second halfof the third postulate is that, after measurement of v yields some eigenvalue a,, the ‘wave function immediately collapses into the corresponding eigenstateauarcummectanileoncpre B Concopeor Wave fren @ @ Postulate 4. Ifa systemis ina state described by a normalized wave function y’, then the average value of the observable corresponding to A is given by (4)=[y'Ay ar Postulate 5. The wavefunction or state function ofa system evolves in time according to the time-dependent Schrodinger equation Probability : Probability of finding a particle withina limit from lower limit to upper limit may be calculated as: yy dt | (y must be normalised) Normalisation Normalisation means to bring a function in normal state. [f a wave function satisfy this equation. Jv'vdr=1, thenitis said to be normalised The limits 4-20 and —co are conventionally used to represent “all space”, although the entire space of a system may not actually extend to infinitely in both directions. The integeal’s limits would be modified to represent the limits of the space a particle inhabits. Wavefuunctions must be multiplied by some constant so that the area under the curve of y#W_ is equal to 1. According to the Born interpretation of y, normalization also guarantees that the probability of particle existing in all space is 100%. In quantum mechanics, y that is obtained by solving wave equation is known as normalised wave func- tion (vary often or generally). We deal here with the mathematical machinery needed to study quantum mechanics. ‘We know that it is possible to multiply y bya constant A to give a new wave funciton, Ay , whichis also solution of wave equation, now the problem is to choose the proper value of, such that the new wave funetion is a normalised funetion in order thavit-} amiormmalised wave function, it must meet the require- ‘ment J (avy (An) 1 = A yydent [4 A where A is normalisation iaSoln. Soln. Soln, — ees a Caleulate the probability that a particle in a 1-D box of length is found to be between Oand 5 (2. nm: Normalised wave function for 1-D boxis| v= yin Therefore, Probability = ig vy i 2 max = VG sin a a For 1-D box; ¥ probability An electrons trapped in |-D region of length 1.0x10""°m. Inthe ground state what is the probability of finding an electronin the region x, = 9.0910" to x, = 0.1101 For ground state of 1-D box n=, First excited state of -D boxn f cx. 5 ie nix in in £ é sinx.sin x dx] = fin’ xdx _{0.110-009)x10"% 1, 2x(o.110x10"*) 2 eloorx"}} 2 aa 110" 1x1 1 =0.02-__ [0,637 ~0.536] = f paaual }=0.004 = 0.40% In the frst excited state, what isthe probability of finding a electron betweenx=0 and x = 0.250%107 arin [A box. v FE int for 1-D b = 5 sin -D box! esi (for l-D box) 12Quantum mechanical concepts & Concepts of Wave functions Soln. Here first excited state is cosidered, so n=2 [CSIR-NET June 2012] 2 os ) 2 Qa On Given that x fink? Pe CRU ent, W =i sue 1 -gareerendeavour.com = Psi lw Ve T 5 2 pen gtx 5 My Flu 38 ce 2 pes 2 pes 1-cos2ax > hee sin 2ax > Fhe [fea > fer aet] AL(3e ‘) ( Steere cae > => |-—| sin 2a~—~sin—— a4 4) 2a 4 2Quantum mechanical concepts & Concepts of Wave functions Qua = o-2 sind sin ve = an 5 5 {For ground staten= 1] u Correct answer is (b) 5. Awave fitation gione by Soln, [vce So, the function is unnormalised. To normalise this wave function, a: coma taken wit the fanetion and now fanetion bocomes (Avj=¥" 2S So, sccomgtothcontgn ofsarmasation, Jrvraeat > jve dv=1 [evra ww.bareerendeavour.c Sol =A 2 Jude x 6. Apatticleis confined «ato +a and gives wavefimetion cos {sit normalised? not normalise it 7 Go mx ax ‘dt = | cos cos—— dx Jrvde Joyce feos! Fac [Jouto- 9828] 2a 2Quantum mechanical concepts & Concepts of Wave functions = i 7 -a) 4 sf 22 nC] ae 20+ [sinz-sin(-r)] i ama 2 © sin(—~ ar ; sat 4 fsina + a+ [sine +sinz] sin x] 2asin x . an ‘Therefore, function isnot normalised. To benormalised, y'= Ay =a+0=a a fav" ay a= => # fyvae=t => As Jv “ particle in a’ 1-D box of length b(Osx > . 4 > So, the function yi orthogonal Ws Correct option is (c) . WWW. Careerwe auaneummachanzalconapts Bconeny of ave nations a ww ‘Operator common | Cartesian component | General definition stunt | Dimeason | fax Per ™ ou Position » Z=z = General General Ism-—Ns | (MILT Hlectromagneticfielduses | Jsm-=Ns | [MI[LIET]" kinetic momentum, A=. =~inV—gA J ([MIELP(T}? Kinetic nergy Clectromagneticfield | Electromagnetic field (A= T (MIELPIT]* vector potential) febe 2m 1 Se (-iRV a) (i894) =f (0-24) Rotation (I= moment Rotation 7 [MIILFIT)* of inertiaa Cuaream mecha concepts Aconcptectoveturctins aa Operator ~] (coramansanie(s} | Cartesian component General definition | Stunit Dimension 1 2. 3. 7 T Potent ney F=V(rt)=V —_— Time-dependent T | Merny potential Total energy 4 (MILL PUT? Hamiltonian 5. (MILPIT Angular momentum 6 operator A pon ih fk Is (MIELPETI? - N Spi angular Where, & isthe sort ‘momentum, vector whose components are the Pauli matrices ‘Aré the pauli matrices for F2i+8 Js UMIELECT? Tost enum [tm pres h N 8. gular momentum ectreVete | go deg Ga) TTT Transition dipole 2 momeni(electric)sions Quantum mechanical concepts & Concepts of Wave functions =. The wavefinetion of I-D hamonic oscillator between x = 400 to x =-o0 is given by f, = N(2x* - 1) Find the value of N if f, is normalised fiction f I alae? 1 ers tag Show that the wave functions fi are orthogonal and normalized, The probability of finding the electron between 0 to 2a, for Is orbital of H-atom, R= er a? (2) 32% (0) 76% (0) 64% (84% P) mat Ifwenormalize the wavefunction | |~€"° €" in three dimimensional spherical coordinate the normaliza- \Bo/ tion constant is La ee ie 1 ©) Don a? © in a gma OF An electron is moving freely inside a one-dimensional infinite potential box with walls at x=0 andx=a. Ifthe electron is initially in the ground state (n= 1) of the box and ifwe suddenly quadruple the size of the box (i.e. the right-hand side walls moved instantaneously from x= ato x=4a). Probability of finding theelectron in the ground state ofthe new box is (2) 5.8% (b) 18% (c) 1.6% @m ‘The quantum-mechanical probability of finding the particle ina one-dimensional ‘box’ in the middlethird of the ‘box’ for first excited state is: (a)0.20 () 0.40 (c) 0.60 (a)0.33 Three real function yi ay Wi ive ised ad Ottgp ail ao lize constant of the wave function By, 2 Ys 1 1 1 iB OR OY OD OF ‘The quantum mechanical probability of finding the particle in I-D box in the middle third of the boxis 1/3 for @) fist level (b) second level (6) third level (@)Never £ L Probability of finding the particle in 3-D cubic box between the limit OSX <7, 0 Ox Soln. Since, we know that, [4,B]y = aBy - Bay = nite? ein aM ny cine y > in3x? haa 43 ad Qi 3xh 2 ith 2a Correct options (a)7. Whatisttevateot # A(x] ix Operators Opera Soin, Let function = f(x) Prge= (Seal $e ‘i (x)= (Ener bys] wtb ets s(syert see 1) reo Ly bye 19 ]oxL stor) “S) foegsorres )erL (ner flo =xxf(x)~ [drtasrtas Fg =27(2)- «pay qaredmageyess com Sola == fs Jax? f(x)- wEF9)-F0) gerne) # f (x)=! [fe x= il () 28 {See art) 9. Giventhat 4 oS: B=2", show that @[# se)]e[4r0)] (b) AB f(s) #84 f(a) Or, show that A,B are anticommutes. son) # f(o)=Ad fe) S200) sh")10. Soln, Hermitian Adjoint of Operators(t) : Every operator can he represented a square matrix: ‘Therefore, Hermitianadjoint ofan operator correspond to conjugate transpose of'a matrix. It is denoted by General Property: (1) (A+B) = at 4 (a) =4 @) (4a) = Btat @(ay (ay (8) ABCD|y)'=(y|DIC'B A’. (© (a Ay =a At Hermitian Operator Anoperator A issaid to be hermitian if At = According to secoind postulate to every observable in classical mechanic, there comespondsan Her- rifian operatorin quantum mechanics. Anoperator A is said to be hermitian if Ju Ayae =|(4v) ydr Eigen value of Hermitian operator are real and eigen fiction of Hermitian operator are orthogonal Show that eigen value of Hermitian operator are real. VOLE CE 7 According to postulate (Mani feacue LEDC ANAM GON ca with he operator A , give only observed value that are eigen value of A Foraeigen value equation Ay =ay a) Multiplying y" both side and integrating equation (1), Ju'aydr=afy'yde =a 2 Now, complex conjugate of equation (1) is taken, So, dy"=a'y’ ‘Multiply it from right side by y and integrate, [Ay'yde =a [y'yde =a 3) If function Ais Hermitian, the left side of equation (2) and (3) are same [=e]Operators Ope It indicates the eigen vaiue must be real nL ‘The eigenfunction of Hermitian operator ae orthogonal Vo () Soln AY = Oy 2) Multiplying, Y.. from eft side of equation (1) and integrate, = Iuidyde=fvlau,de om) take the complex conjugate of equation (2), Multiply by y, fromright hand side and integrate it. > favnde=a, fyiv.de a) Ifoperatoris Hermitian the LHS. ofboth (3) and (4) are equal Jawiv.ds = a fyiy dx 2 [e: a)fys (| IW m=n,(a,-4,)[yivide=0, a2 = a3 [yay d= : nem,(a,-a,)#0, rl ete | Thisis condition of orthogonality ousoal ‘Quantum mechanical operatorsare hermiian operators A hermitian operator 4 obeys the relation [oe Agde ={(4f)* eae = J(A*/*)gdr. (Property ofhermitian operator) Where dr is volume efement. For example ‘r ’ represents the Cartesian coordinates of particie that cant move in three dimensions, the integralsis a three-fold integraland dv stands for (dxdydz) . The symbot /** dS SER CORRELL RAGUSA, and 4* denotes the complex conjugate ofthe operator A. zexely here the real quantity xis called the real part of z and the real quantity of y is called the imaginary part of z ‘The complex conjugate of any complex number, finction, or operator is obtained by changing the signofits imaginary part fhe et mox-ly Sol Areal quantity ora real operator is equal to its complex conjugate, and an imaginary quantity or an imaginary operator is equal to the negative ofits complex conjugate, ‘Thus, wecan write the definition of a Hermitian operatoras an operator that satisfies the retation fl stags = [0p At pte (0) where f(x) is any well-behaved function.Operators. 11, Prove that the kinetic energy operator is Hermitian wd 2m ds? Soln, Asalways, we shall assume that function vanishes at infinity. Thus, following the procedure of integrating by parts twice. : (ros meee seas) fromlefthandside, 7 Mo am lo! are fromright hand side, wn capeprgndeavour COM ox ax LHS=RHS Hence, kinetic energy operator is hermitian. 12, Showthat , operators hermitian. son, J Sp, fae=["F olf ae Left hand side, Right hand side Iir(as)e-Co(mg) ra =n Lar inf LasOperators Op = inf” r fac so Of” = anf? Lae Rignmandside eo" Ox LHS=RHS, So, P, ishernitian operator. Note: CLS F1E <0 because boundary condition and function vanished at boundary It also give particular value at 40 t9 — 20 So, itis zero, 15, Of als al ax Eigen function and Eigen value equation Eigen value equations are those equations in which on the operating ofa function by an operator, we get function back only mukipled bya constant value. The function i called eign function and the coustan valves called eigen value - 13, Show that e is the eigen function ofoperator, (INU Ph.D. 2012} : Solr = 0 because function vanishes 2 infinite. Sot Db" {tension i ‘respect to x(n times). 1. Therefore, ¢* isthe eigen function of operator 0. Sot 14, Show that cos ar cos by cos cz isthe eigen function ofthe operator scosbyeoses ar13 ue get eis Operators a aq 15. Soln, Soln. 17, Soln: 18, Soin, 6a aa by cos ce—— cosaxcosce—— cos by by Ze cosbycosee = = -cosax + y+ cosaxcosby <= coscz oy a 7 sinax) cosaroser (bsindy) sosncnsby © (eens) = c05by'c0s.cz(~a” cos.ax) + cosaxcosce(-b? cosby)+ cosaxcosby(-c* coscz) = -a’ cos ax cosbycoscz + —b” cos arcos by cosez + —c” cosaxcosbycoscz =-(a? +8 +2 \(cosax.cosby.coscz) Therefore, eigen value =~(a" +5? +c") Show that ¢'* isan eigen function of momentum operator. What is the eigen value? ‘Therefore, ¢ is an Eigen functio Ife" acigen function; ifitis so; then’ d a iat orf) Al’), HF Py 3h ayant 3a? de ¢” is an eigen function ofthe operator -t6') ‘The corresponding eigen value is @+4 (0) 4 (o) #2 @2 IGATE 2013) 2 a Given, e?*" is aneigen function of the operator (aeSoin. 20. 21. Soln, ae (a oe a = 16x? a e wo ©. 7 S| aye |-i6x%e > Ae +(-4x)(~Ax)e?*” -1oxte™ u Bis > —de™ +16x%e* 16x70 5 ag? gan ‘Therefore, 6°®* isan eiget Correct option is (b) Show that p, is hermitian bi (,)' Show that k =~" 2 itnermitian by.using the concept ofhermitian adjoit ,careerendeavour.com (28) 8 2\ 2) we 2-5] s- Sok, ax) ae, 2m ax* So, kinetic energy is hermitian. ‘The hermitian conjugate of operator d/dx, called (d/ dx)" isactually equal to (@) -d/dx (b) did (itdidx) (@) “(aiex) Hermitian conjugate or adjoint ofan operator A is written as A\', and is defined as Operators {NET June 2011]st 22. Soln. (é Correct answer: (a) LfAis hermitian and B is hermitian then, show the commutator. [4a =(49y (24) =BtA' —A'B! = Bt A'—4'B'=BA- AB=[B,A]=-[4,B] ‘Then commutator oftwo operator is antihermitian, Average value or expectation value = Jw 'Avar (all space) Uncertainty in the physical observable correspond to A. pieces. Af‘ xcos2 spespanygc™ com e te Quax ‘é | os | ve Lee 2 i [fcos 28] é loOpe a 2 24. “il: in 21 © feos 3a ~c080] Ann |, Anta = jeg] ts in + perso 4nn é é ann Soli =7Ui) sin in ME a = Fin nl cos 25, Sol 2s cayeparrinag we £ a 26 titi Ll a8 ¢ é So w) ea z aZlP e 2n7x dxOperators 24. Soln, 25, Soln. 26. Soln. a Consider a particle of mass m, moving in 1-D box under the potential V=0, 0 x €, calcalate the average : 2 nex value ofenergy using v= sin ~~ é 22 sin 2H ln Ey £ (2m ax? £ mx 2hnth? f nax nex BI gy =e fi ¢ ¢ Ime £ a Wnt nth? “tlm? 2 Im 42m e ~ &me ‘The function N, (a” — x’) is defined for the interval x =—a to x = +a find the value of [IN (@-2) (et) > me x Find for ID box, y = (¢-x)x,0 $x$ ¢ isnormalized ornot ifnot then normalised it and find average energy Jix(e-a)a(t-a)ae = [52 (xt 208) de = filet ext -20r ar = [Peace [stae-2f' ode ee ee - ELBE 3 Si ay Pre ie > eff ST 3] 5 4Operators Oe +667 -158 30 30 SO, Voomtise = 97" 27. The state ofpartcl in free stateis represented by y (x)= Ne”. Find outte factor. Soln, This is @ normalised function, Toten" olara_ 28. “drsinadods \www.careerendeavour.com Soln, vp Theconditionofnormalisation, | ¥ ¥"dt =1 i ere ; > 2 Axx2 Now, Juy'de= fe" e'anr'dr =4nfe™ i? de = any mea a 2 a 2 2x2 ) So, the given function is nat normalised Let the normalised function is y "= Ay (: J Ay ay'a d [4e" Ae anrtdr =1 2 i)Operators Gi LS Therefore, the normalised wave function: "= (i Average value ofr: ()=Jtvrdr = iE & nf e4nr'dr a aa " -‘tjem [amafeene Eq 0 a4 BL 44302 3 2" xdxIx2 2 (ii) Average value of a 7s G-AE (ii) Average value ot(e) : ant 4 ae ()=F]re (ars 4x4x3x2x1 2x2x2x2x2 Average value of Kinetic Energy (E): Normalised wave function for Simple Harmonie Oscillation getOperators Op Sol iw 2) Jiv{ zero point energy) / Ba[n E> au 2 ot |F 2a 4 Vm Seer Ee 420 4 Average value of Potential Energy (V): vedix! mle ono B) BY Fs oe (ef gh fe eras (4) lien ee Solr ‘Ghee FES] t serendeavour cor Orthonormal condition : Ifeswo wave finetion W, and y, (ory, and y,) aresuchthat fy;y,de=0 or [ysy,de=0 ‘Then y,, and y,, are said to be orthogonal. If m=n; inthis condition then Jvivade=1 (normalised) and fyiy.de=t (normalised) A set ofinction that ae both normalised and orthogonalto each other iscaled aorthonormal set. We can express the condition such that 8-0 (iri 3 B= Junie il 8,=1 (i=))} | (Kronecker Delta)Operators ISOLVED PROBLEM! 1. Show that wave function for different set mand n for a ‘ona in -D boxis orthogonalto each other. (2. max [2 HX 4 nt mB max In. = sin and y, ~ sin de Son. Va =p sin and y, = sin «|? = fasnttt sin waft ste 7 [sin(m—n)xsin0] (m=n)a- => — fyiy.dr=0 So, Yq, and y, are orthogonal to each other. 2. Show that wave function fér Is and 2s orbital of H-atom are orthogonal. Son, %.= ye and V; t|2-7 {6% Son Tn ob Ya? wa , are orthogonal to each other. 3 Show that the wave finetions, f,(x}=N,(a?—x") and f,(x)=W,x(a?-x7) forabounded region -a -0 (A=KH) @aAt=a Aisconstant ofmotion (ie,, doesnot change with time) if Sor-jllatryo(}-o ee poy . aA s If A istime independent [ & G=0 ] then; for A tobe constant of motion, glaiy-0 a, (Ga-0 Note: If A,ti|=0 , then also we can say Aisa constant of motion.Boars In each case, show that x) is an eigenfunction of the operator given, find the eigenvalue. A f(x) 6a) 2. OR coseox d joe OF e 2 © Stas em é OF xe d ap OR Hint: Be sure to include f{x) before cartying out the operations. The Hamiltonian operator for asysteimis H =—(I Brim)! 4x3 + yh 2? For this system we should expect- (@) two quantum numbers at most ax (b) eigenfunctions that are sumis of functions, each depending on only one of the variables. (©) cigenvalues that are products of eigenvalues of separated equations (d) cigenvatues that are sums of eigenvalues of separated equations. (e) note of the above is a comect stateinent. What are the expressions for the following operators? cea OE ) Which of the following operators are linear? > ~ A a @ 4p =i9 ) Cpa? Git) Bp = i (Asconstant) , @ Which ofthe functions sin 3x, 6c0s4x, 5x°, 4, 3e°*, in2x are ‘eigenfunctions of we x foccachelgenfimction state the eigenvalue. Show that ifA is hermitian and B is hermitian then its product AB are hermitian, iftheyare commute. Show that operator 4=i(x? + ye ix is hermitian, Ifthe y,,.., are the eigenfunction of the operator L +L’. then what is the eigenvalue, fa {eee (>) meta? (© EGHA? +mA? @) eee - meh? u 13 14. 18, 19, 20,Operators 10. 13 14, 18. Given two hermitian operator A and B. We construct the following three additional operator, AB, ABA, A’B and AB? Choose the correct option as below (2) Allthese four operator are hermitian (b) Only3 of theseare hermitian, (6) Only two of these are hermitian (a) Only one of the operator is hermitian, 2 1 7 For Eigen function + sin 3,63, the eigenvalue of operator "2 jg 8a°m dx y2 2 \2 42 2 2 ae 3.63) hi 3.63) h’ (3.63) h’ —(3.63) h’ ee cc pc 8x'm 8x°m 8x°m 8n°m pada) If A= and B=? Evaluate the commutator |. dx 8] Find the value of commutator of hamiltonian in x-direction with position x. Pe ‘When the operator ~-=5-, operates onthe fnction ¢-,theresult i é (a) Rte * oy inte ik (@ Re™ ol. (2. nx For eigenfunction fi = pny a he Ve Les of particle in a 1-D box of length b (0<.x % 23, Theset ofeigentimctions ,/ sin“=*(0-5 x Booskl =0 ie. B= or coske=0 2Asinke=0 = Asink#=0 ie. A=0 or sinke=0 0 1 Probability densityPossible solutions; Particle in a Box Parti (@) 4=0,00skl=0= kant oka (nal35, () B=Osinkl=0 klar katt (022,46, Soln, so, v (x)= io 2) fo Fornormalised function, fy%dr=t en ee = fl asin et >» # [teat 2 = al poandp conte = 1 Lo. nax Therefore, Horne = gS (Nn 2,4, 6, Soln, Soln,Particle ina Box x qi Soin, Soln. Soln, SOLVED PROBLEM: The probability of finding a free particle inside the left halfofa 1-D box oflength Lis [GATE 2002] - @Le © 42 . OF au £ 2 4 (2. nex Normalised wavefunction for -D box is | ¥ = sin“ , __, left-half —right-hal ‘Therefore, Probability = [ovvac [2 iq WOOL For 1-D box; Y=" probability = Cf i s ‘ a2 PBL gy 21 (ggg mee, 2 BQ ERLE 2b an For the energy level ~+; the probability for a particle of mass ‘in over the ength ‘a’ of a 1-D box is depicted mai) 2 Uae a IGATE:: 2003] 8ma? ma’ ¥ sme a ial a4 x=0) rea x=0 3 node, 4 maxima. Inunit of

the energy diference between level corresponding to3 and 2 node eigen imcton, fora mi particle of mass ‘m’ ina I-D box of length /is [GATE 2004] node number = n= er For 3-1 =4, B= ‘or Ssnodesn=4, B= 9p er node; n=3, Ey=——— And for2-node; n=3, B=— 7ParticleinaBox Part ae se =o = (16-9 8mé> me? (16-9) 4. Find the first excited state wave fietion for a particle in abox that spans ffom-ato +a. [GATE : 2006] Sola. Fora particle ina box from ato ta, Soln. Wave functions To { na x)= [sin] 2 v.ta)=fEsin() For the excited state, n=2. Then i (2) y=-sin| = aka : 05h 5. Plotthe graph ofa wave function aving energy —=>~. a = ean? ‘This coresonsto ist excited slatehaving | noes at ¥=5 9. 6, Tfaclectronescaped in a 1-D box of length 1A having energy 608.4 eV, plot it’s graph. ASE Soln whe 9 Son, y= 6084x1.6x10" Joule 608.4%1.6%10-? x8x9.1x10' x(10™) ns (60x10 =16.17 n=Ji6.17 =4 7. Apatticle is confined to a 1-D box oflength I mm. Ifength is changed by 10.” im, the % ofchange in energy in the ground state. Sayey 7 [GATE-2008] 10. aed 1 Soln. Percentage of change in energy inthe ground state: “100; um ee |aB}x100 4m? % ofchange inenergy = [e}x100 ame E wi ie i, 2g - 4 (- 4 = [prelo? x100= 2x10 (-4e=10") 8 Considera ball ofmass 1 g moving with aspeed | ems‘ ina one dimensional box of edge length equal to 1ocm. Soln (1) Caloulate its kinetic energy and the number n corresponding to this kinetic energy.iS Partcleinao« (2) Ifthe ballis to be promoted to the next higher qunatum level, then how much of energy s required ? Formthe obtained value justify that the kinetic energy of. larger mass varies in a continuous manner and can be calculated from the classical mechanical laws of Newton, Uy) esa ale) eee 2 mns"y? Sola. (1) Kinet energy ofthe ball (mv 5 |(U0°ke)(10" ms")? = 0,5 x 10-7 kg mts? =0.5 « LO". Since, (0.5107 JY8\LO"'m)* is Theref ae 2 FBR) OO AO LEO ay CORD) <9, 11310 an @IBF mk (6.62610 sy R Q) Now, Af=£,,,-£, =(2n+1) 8Pm (6.62610 Js) = (2% 3.02510 1) 6626-10 J)" | 3 ( {een Poa 9, Anelectron is confined ina 1-D box of length of 1A. Ifelectron fall from first excited state to ground state, what energy it will emitt? Soln. Length ofbox, (= 1A =107 m PRR Energy of I" excited state, E, = ——> = Bml™ &ml ae Energy of 2" excited stat a rey of 2* excited state, Hy = 5 = ae =(4-)— 8me = (3x37.6)eV =112.8 eV 10, Aball ofmass 1 gm confine: (principle quantum nuriiber Soln, We know the energy of l-D box = It’s kinetic energy. we Ly 8me? 2 4(10°)' x(0.01)' x(0.1)° (6.627x10*)" = 9.13107 n= 9x10" (Quantum numbern is very very large. It is not possible to calculate the difference between successive energy level. So, itis not possible to observe quantization in the energy level . IL An electron of mass “m’ is confined to a one dimensional! box of length ‘b’. If it makes a radiative transi- tion from second excited state to the ground state, the frequency of the photon emitted is oh. 3h h (@ Smb? ) Smb? One (@) Soln Energy for one-dimensional box is a GATE 2010] mb? fevParticle ina Box 12. Soln. R For ground state(n=1), B,= gg one For second excited state (n=3), By = oy one 8 AE=E,~E,=—-— = 3 Sab Bb Bnd? B “nb Since, we know that, AB = hy v h Ivey = y= ee Correct option is (¢) ‘The wavefunction fora quantum mechanica partical ina 1-D box oflengtha’is given by y = Asin™*. The : a valueof ‘4’ fora box of length 200 nm is IGATE : 2011] (a) 4x 10% (rm)? (b) 102 (nm)! (e) V2 O(mm)!*@).0.1(nm)"* Given that fumetion v= Asin = (= a= 200mm) ¢ Fornormalized, wavefunction fi asin™ asin ae =1 J a @ Correct answeris (4), Particle in Two dimensional Box ‘The mathematical form of potential for 2-D box: V(xy)=0 O X(x) Ox ae =0 Rak HEX (x) =0 _1_ &¥(y) aoe ¥(y) ay" 7 SO) er y, ~Q) Way Solution ofequation (2), x (x 242 Solution of equation (3), ¥{y)= E sinh? and E22 - Fs [Eg uy vee, Noi GZ