Quantum mechanics is a branch of science of motion of micro like atoms, protons electrons (Subatomic Particles) particles etc. Its study is important because of physicochemical properties atoms and molecules, structures, spectral behaviour and even reactions can be interpreted in terms of the motion of micro particles. The branch of science based on Newton's laws of motion and Maxwell’s electromagnetic wave theory to explain phenomena related to motion and energy is known as classical mechanics. Classical mechanics could not explain the phenomena like black body radiation spectrum, heat capacity of solids, photoelectric effect, atomic and molecular spectra etc. Development of quantum mechanics starts with Planck’s quantum theary which was following by de Broglie’s hypothesis of matter waves and Heisenberg uncertainty principle. Schrodinger’s wave equation leads to the formulation of wave mechanics.First Law Every body remains in a State of rest or uniform motion unless acted upon by a net external force Second Law oo The arnount of a eration of a body is proportional to the acting force and Inversely propertional to the mats of the body. > a Third Law z sut Opposite reaction. rit on object B, then object 8 will exert an equal but opposite force on object A.NEWTON'S | | FIRST LAW OF NI MOTION — ‘An object at rest well romain at rest Deut a en er ced object and the amount of force appliedExamples of Newton’s Laws les es First Law Second Law Third Law An object wants to The acceleration of Applying force to an remain in its an object generates object results in an Co ae ae oh Cee ee ec ae mera direction ilkBave anew theory called electromagnetic theory. In his theory he developed a set of four equations called Maxwell's equations. Using these equations he predicted the existence of electromagnetic waves. He also calculated the speed of electromagnetic waves which was similar to the speed of light and said that light is an electromagnetic wave.é Maxwell’s Theory Electricity and magnetism were originally thought to be unrelated Maxwell's theory showed a close relationship between all electric and magnetic phenomena and proved that electric and magnetic fields play symmetric roles in nature Maxwell hypothesized that a changing electric field would produce a magnetic field He calculated the speed of light — 3x10* m/s — and concluded that light and other electromagnetic waves consist of fluctuating electric and magnetic fields ie 1831-1‘Comparison of Classical Mechanics with Quantum Mechanics Classical Mechanics ‘Quantum Mechanics i) It deals with macroscopic particles i) It deals with microscopic particles ii) It is based on the Newton's laws of ii) It is based on de Broglie’s concept and motion Heisenberg’s uncertainty principle iii) It is based on Maxwell’s electromagnetic iii) It is based on Planck’s quantum wave theory according to which energy theory according to which energy is emitted or absorbed continuously is emitted or absorbed not continuously but discretely iv)The position and velocity (or momentum) iv) It gives the probability of finding of the particle is defined precisely and a particle at various point in space simultaneouslyAtomic OrbitalAtomic OrbitalElectron shellAtomic StructureBlack Body Radiations Radiation (electromagnetic wave) is emitted by any solid at any temperature as a result of vibrations of its particles. Different solids emit radiation at different rates at the same temperature; the rate is the maximum when the solid is perfectly black. A black body absorbs all the radiatian that falls on it and retains all the radiant energy, For experimental purposes, a black body is generally a blackened metallic surface, a hallow sphere, blackened inside with a hole. All the radiations entering through the hole are absorbed completely by successive reflections inside the enclosure.Incident tadiation Small hole or opening (N) Projection (C): stops direct reflection of normally incident tadiationT3 T3>T,>Ti Energy ———» | tw Wavelength ¢ >) ————» Fig. 5.1 Spectral distribution of radiation from a black body at various temperaturesro Weavelenge {nm}Cea cee Ele) 1 s 3 spectral irradiance (kW/m?/nm) ee CE TC wavelength (nm)Rl Peel om Ce CR UL STL ae) Pre ou Ay Ta mt Sac DT ry ECU SoA en the fictitious fort Cus lee SuA black body is not only a perfect absorber of radiant energy, but also an idealized radiator. The radiation energy emerging from the hole will also be very nearly equal to that of the black body. The energy emitted from the black body depends only on temperature (T) and is independent of the nature of the solid. The dependence of radiant energy density on temperature and wave length is shown in Fig. 1.1. The classical mechanics fails to explain the energy distribution of black body radiation. Max Planck in 1900 explained the energy distribution of black body radiation and was awarded a Nobel prize in Physics in 1918 for proposing the quantum theory of radiation.Characteristics of the curves For each temperature there is a particular wavelength at which energy radiated is the maximum. With increase of temperature, the position of the maximum shift towards the lower wavelength. Higher the temperature, more pronounced is the maximum.Planck’s Quantum Theory of Radiation In 1900, Max Planck studied the spectral lines obtained from radiation emitted by hot black body at different temperatures and put forward a theory known as Planck’s quantum theory of radiation, The various postulates of this theory are: 1. A hot body emits radiant energy not continuously (not as continuous wave) but discontinuously or discretely. In other words, a hot body emits radiant energy not as continuous wave but as small packets or bundles or discrete unit of waves. Each of this unit is called a quantum (plural quanta) which can exist independently.Fig. 5.2 a) ) @ b) Emission of radiant energy from heated metal ball Continuous waves (according to Classical old theory) Discontinuous waves (according to Planck's quantum theory)The energy associated with each quantum or photon (in case of light) is proportional to the frequency (v) of emitted radiation, i.e. Eav or E=hv-—- eooneeen (1) Where h = Planck's constant = 6,626 X 10734) 5 v = Frequency of emitted radiation or light in Hz (or CPS) But ve ; Where c = Velocity of light (ms) A = Wavelength of radiation (m) The energy emitted or absorbed by a can be either equal to one quantum of energy (hv) or any whole number multiple of it, i.e. E=nhv---—------- ---- (3) Where n= 1, 2,3... Thus energy emitted or absorbed by a body cab be equal to hv, 2 hy, 3 hv étc. but never equal to fractional value of hv like 1.2 hv, 2.7 hy, 3.6 hv etc. Thus the energy emitted or absorbed is quantized and this is called the concept of quantization of energy.Applications: It is used To explain the photoelectric effect (1905) To develop Bohr’s structure of atomic model (1913) To explain the Compton effect, i.e. scattering of x- rays (1923).Photoelectric Effect The phenomenon of emission of electrons from the metal surface when light of suitable wavelength falls on it is known as photoelectric effect. The emitted electrons are called photoelectrons.his became known as the photoelectric effect, and it would be understood in 1905 by a young scientist named Albert Einstein. Einstein's fascination with science began when he was 4 or 5, and first saw a magnetic compass.Fig. 5.3 Photoelectric effect ExperimentFig.1.3 illustrates an apparatus for demonstrating the photoelectric effect. In a highly evacuated tube, when a beam of UV light falls on the metal surface M, electrons are ejected from the surface. These electrons are pulled to the anode P by high voltage V, thus completing the circuit. The flow of current is measured by a galvanometer G.Vo Frequency ———» 4 Fig.5.4 Vanation of K.E. of the photoelectrons with frequency of the incident radiationThis current is known as photoelectric current. After studying the photoelectric effect carefully, the following observations are made: 1. For each metal there is a minimum frequency of incident light below which no electrons are ejected or emitted. This is known as threshold frequency, Uy. The threshold frequency is different for different metals. 2, The kinetic energy (or velocity) of the emitted electrons is independent on the intensity of incident light but is directly proportional its frequency. 3. The number of ejected electrons from the metal surface depends on the intensity of incident light. The greater the intensity, the larger is the number of ejected electrons. The photoelectric effect was explained by Einstein (1905) on the basis of Planck’s quantum theory of radiation. According to quantum theory, the radiation consists of packets of energy called quanta or photons of energy hv, where h is the Planck’s constant and v is the frequency of radiation.Evaculated quartz tubeIncident light ay 4 © ©@— Ejected 4 Photoelectron Metal surfaceWhen a photon of energy hv is incident upon a metal surface, its energy is utilized in two ways: A part of its energy is used up in ejecting the electrons from the metal surface. This energy depends on the nature of the metal and is called work function (ct) of the metal. The remaining part of the photon energy (hv — $) is converted into kinetic energy of the ejected electrons. Thus 1 iy? hve tomy Where m = Mass of the electron and v = Velocity of the electron But =h vo — Where vo is the threshold frequency. Therefore equation (1) becomes hv=h Vogts mv? 1 hv=h Vos mv? a 1 2 hv-hvo= gm S 2=hv-h zmv? =hy-hvo mv? = hl v-ve) — -==(3) Equation (3) is called the Einstein photoelectric equation. Einstein won Nobel prize in1921 in wi lentiioe Somnus fe ee egCompton Effect (1923) A.H. Compton found that if monochromatic x-rays are allowed to fall on carbon or other light element, the scattered x-rays have wavelength larger than the incident x-rays. The phenomenon in which there is a change in wavelength of scattered x-rays is called Compton Effect. The angle through which the incident x-rays are deflected from their original path is known as angle of scattering and is denoted by 8. Scattered x -rays Scattered photon - . (Energy = hr’ med ) scam rays) ge Angle of scatterng x On i (pees Photon Rest électon (Energy = hy = he Scattered electron a Fig. 5.5 The Compton EffectBy applying the laws of conservation of energy and momentum, and by assuming that x-rays are composed of photon each of which has energy hv, Compton gave the relation @ 3 h 2h. AA= a - A= (1- cos 0) = sin? 2 Where AA = A’ — A = Increase in wavelength = Compton wavelength shift A = Planck's constant c = Velocity of light @ = Angle between incident and scattered x-rays, i.e. angle of scattering Here A‘ > A, i.e. wavelength of scattered x-rays > wavelength of incident x-rays The above equation clearly shows that AA depends on the magnitude of the angle of scattering,@.Case 1: When @ = 0°, AA = 0, i.e. the scattered light is parallel to incident light. . _ ene — he 6625x1074 7 _ Case 2: When @ = 90°, AA = wo baxiptixea’ 2.42 pm (~ cos 90 = 0) 2 x 6.625 x 10734 . = a = Z Case 3: When @=180" , AA= wir Sixio-iixg nior 484 pm (+ cos 180 = —1)De Broglie’s Hypothesis In 1905, Einstein suggested that all electromagnetic radiations including light have a dual character, i.e. particle and wave nature. The diffraction, interference and polarization support the wave nature and photoelectric effect and black body radiation support the particle nature of radiation. In 1924, de Broglie extended the idea of wave- particle duality of light to matter particles. He suggested that all moving material particles like electron, proton, neutron, atom, molecule etc. in motion possesses particle as well as wave characteristics, i.e. dual characteristics. The wave associated with matter particle is called de Broglie’s matter wave.De Broglie’s Equation In 1924, de Broglie suggested that the momentum p of a moving microscopic particle associated with a wavelength A such that hh A= m2 (1) where, h = Planck’s constant m = Mass of the material particle u= Velocity of material particle p =mu= Momentum of the particle Equation (1) is called de Broglie’s Equation.Derivation of de Broglie’s Equation According to Planck’s quantum theory, energy of the photon (light ) is given by E=hv=¥. (1) Where v = Freuency of photon According to Einstein mass energy relationship , energy of photon is given by E=me — —-- (2) Where , m= Mass of the photon c= Velocity of the photon From equation (1) & (2) ,we get or mest me (3) According to de Broglie, ‘a moving material particle (mass = m & velocity = u) exhibits dual character like a photon and hence equation (3) can be applied to it. Momentum (mu) of the particle is given by, or a=te mu Pp h = Planck’s constant A= Wavelength associated with the particle. Equation (4) is called de Broglie’s Equation. The de Broglie’s equation is significant for microscope particles like electron, proton, atom etc. It is insignificant for macroscopic (very large) particle. (4)Heisenberg’s Uncertainty Principle The electron has wave nature. Hence, it is not possible to measure simultaneously its exact position and exact velocity (hence momentum) in space at a given time because wave is extending throughout a region of space. Thus, Heisenberg in 1927 introduced a principle called as Heisenberg’s Uncertainty Principle. Statement: According to Heisenberg, “It is impossible to determine simultaneously both the position & momentum (or velocity) of a small moving microscopic particle like electron with perfect accuracy.” It means that both position and momentum associated with the microscopic particle can not be measured accurately and simultaneously.Mathematical Expression Mathematically , it can be stated as axap > 2 - ~ (1) Where, h = Planck's constant 4x = Uncertainty in the measurement of position of the microscopic particle Op = Uncertainty in the measurement of the momentum of the microscopic particle From equation (1), it is evident that, if Ax is small i.e., if the position of the particle is measured with high accuracy then Ap will be large i-e., the momentum will be measured less accurately & vice versa. If the position of a particle is measured accurately, Ax should be zero and hence. Ap = a D> Gen On This means that error in the determination of the momentum is infinite. If m= Rest mass of the particle Aw= Uncertainty in the measurement of the velocity of the microscopic particle Then Ap =m dv Hence equation (1) becomes ox 6v>— ‘nm. A microscopic particle like electron can not have a definite path due to its wave nature. Some times instead of measuring the position and momentum of the microscopic particle, we measure its energy (E) and time (t) for which the particle remains in that energy state. In such a case, uncertainty principle can be express as ag atet (3) a Where AE & At = Uncertainty in the measurement of energy & time respectively.Bohr theory versus uncertainty principle Uncertainty principle tells us that due to wave nature of electron, we can not described the exact path or position of the electron in an atom at any time. Thus Bohr concept of definite orbits electrons is no valid. In order to describe the position of the electron in an atom the maximum we can do is that we can only predict the probability (or relative chance) of finding the electron in a particular region of space round the nucleus i.e. we can only predict where an electron is most likely to be found. The probability density of finding the electron at any given time is given by w?, where w is the wave function. Uncertainty principle is significant only for microscopic particles like electron, neutron etc. & has no significance for large (macroscopic) particles.Sinusoidal Wave Equation There are two types of waves, running waves (e.g. water waves) and stationary waves (e.g. vibrating string fixed at two ends). Electron waves in atoms or molecules are of stationary type. For stationary waves t) does not vary with time. The equation for stationary wave fixed at x = 0 and x = ais given by The boundary conditions are W = 0, atx =O and x =a. The general solution of equation (1) is given by p= A sin2* + B cos*S* Where A and B are constants. When x= 0, y = 0, thus we have O=A sin222 4 B cos O=AX0+B X1 ne B=0 When x =a, j) = 0, thus we have O=A sin2=* A#0, thus sin=2* = 0 This is true only = = nm, where n= 0, +1, 42,43... 2 Thusk=22 orv= 22 sincev=for S=k n za x v26 36 A€ etc. vibrations are 2a’ 2a' 2a’ 2a * If n = 0, then v = O i.e. there is no vibration. Only v = allowed. Thus by putting the value of B = 0 and 4 = “4 in equation (2), we get pea sin* +B cos*=* =~ (2) yaa sine anx w= A sinSchrodinger wave Equation In 1926, Schrodinger, an Austrian physicist using de Broglie’s idea of matter wave developed the wave equation for electron wave. This madel describes the electron as 3-D standing wave (stationary wave) around the nucleus. Schrodinger proposed that since electron has wave like nature, it should obey the same classical wave equation of motion as the other waves. On the basis of this idea he derived an equation which describes the wave motion of electron & is known as Schrodinger’s wave equation. ty 8 ay a ay 8m x? xt t ye at oe 2 ryt a (E-Vyy =0 Where w = Mathematical function called wave function E = Total energy of the electron V = Potential energy of the electron m = Mass of the electron h=Planck’s constant 2207? 0? a? . v= et a + 3p Laplacian operator ( read as nabla operator) Schrodinger equation is a differential equation of second order. (E-V)y =0Derivation of Schrodinger Wave Equation in one Dimension The wave motion of a wave of a vibrating string can be described by the equation y= sin (1) Where w = Amplitude of a wave called wave function A= Constant x = Displacement of the wave A = Wavelength of the wave Differentiating equation (1) w. r. t. x, we get dp 210A 2mx Ge SQ (2) Differentiating again equation (2), we get ay an\? . 2x a -G) (4sin27*) ap amp 7 wt 0 (3)Since an electron in an atom described as a standing wave round the nucleus, the classical wave equation (3) which describes the wave motion of any particle vibrating along x-direction should be applicable to the standing wave of an electron. From de Broglie’s hypothesis, A= + ap amt “oe tae =O The total energy of the electron is given by E = Kinetic energy + Potential energy 7 . muz+V ie. m*’u2=2m(E-V)-- -- (5) Substituting the value of m?u* from equation (5) in equation (4), we get ay | antm _ wot te (E-V)b=0 ~ Equation (6) is the Schrodinger’s wave equation of a wave moving in one dimensional space (along x-axis)For the wave motion in a three dimensional space (3-D), the Schrodinger equation take the form. 2 2 2 0 a Oty 8m 7? Soe ot Set SE (e-vw=0 0-0) ami? y+ SE (E-V)y =0 —————-(8) Equation (8) can be also written as at (— sar + V)W=ED- =) The Hamiltonian operator H is defined as = h? p2 a= — D+ V (10) In terms of Hamiltonian operator, the Schrodinger’s equation can be written as Hp=Ep- ~ (11) Schrodinger’s wave equation is the second order differential equation. Therefore it has several solutions for 1! but many of these solutions are imaginary and hence are not valid, Only those values for y) are acceptable which satisfy following conditions:The wave function w must be single valued i.e. it must have one and only one value at a particular point. i gs cnet GY dy dy The wave function w and its first derivative — , —,— must be dx! dy" dz finite and continuous functions. The value of E obtained by substituting the acceptable values of 1) in the Schrodinger wave equation are called eigen values of the function w's which are called eigen functions. Thus in Schrodinder’s wave equation E values are called eigen values while yw values are called eigen function. The eigen function for an electron in an atom is called as atomic orbital. The eigen functions are normalized and orthogonal. The wave function wp is called normalized if fj jdt = 1 (i=)) and orthogonal if f 7 yj dr = 0 (i+#/).Physical Significance of w (the wave function): First Interpretation: This interpretation was given by Schrodiger himself. The wave function wy), itsif has no physical significance except that it represents the amplitude of the wave. In studying (dealing) with all forms of wave motion such as light waves, sound waves or matter waves, the square of amplitude of the wave (i.e. i") at any point represent the density or intensity of wave i.e. the number of waves per unit volume. Therefore, the value of yy ("y) at any point around the nucleus is the measure of charge density ( particle density) for electron. Second Interpretation: Born ini926 gave statistical interpretation of yy. He awarded a Nobel prize in 1954 for his interpretation of y. According to this interpretation, | ye | represents the probability per unit volume of finding the particle at that point at a given instant. If yp is the wave function of a particle, then the probability of finding the particle within the range from r to r + dr is given by wr dr= lp? dr Where ip* represents the complex conjugate of ip. y)? is always real. If =a +ib, then wy" ib. Therefore, p"y=a? + b?,i= v-1.Applications of Schrodinger’s Wave Equation This equation has been used to calculate energy & wave function of a freely moving particle in a one dimensional box This equation has been used to calculate energy & wave function of a freely moving particle in three dimensional box This equation has been used to derive an equation for energy of an electron in hydrogen & H— like atoms.Energy of a Particle in a One Dimensional Box Let us consider a particle (say e- of mass m ) is confined to move ina one dimensional box of length a & having hard walls of infinite height. Suppose move along x-direction & is confined between x = 0 & x = a. Potential energy (V) of the particle inside the box is zero. Thus, there is no restriction on movement of the particle within the box. Outside the box V = °%, i.e. V = 00, atx <0, x 2a, V=Oin x =0 tox =a. Therefore 2, i.e. the probability of finding the particle is cor ico 1 i rT. ~T vaco v=o sn ¥=0 zw =0 P re =o as ¥=0 y=0 Fig.: Particle (dot) in 1-D boxSchrodinger’s wave equation for 1-D box is given by is @y | smn + RE CE -V)y = 0 (1) AS v = 0, we have @y | smi oY AE py =0-————- (2) ey ay = Or Ga + key — woceeneecesnneeee (3) Where k? = aE srceeceseneeeeo= (4) The solution of 2"4 order differential equation (3) is given by We=Asinkx+Bcoskx = ------------ (5) Where A and B are constants Now applying the boundary condition when x = 0, ) = 0, hence from equation (5), we get B=0 Putting B = 0 in equation (5), we get W=Asin kx seeeccceaasnsnees (6)Applying other boundary condition for equation (6), we get When x=a, p=0 Thus 0 = A sin ka Since A #0 (if A = 0, tb2=0 every where in the box which is not possible) -. sin ka = 0. This is possible if ka = nz (n is an integer) Thus ka =n 7 2 eae (4) Comparing equations (4) and (8), we get Bm 7? Pa (9) Equation (9) gives the energy of the particle in 1-D box. From equation (9), it is observed that energy of a particle is quantized. All values of E are not allowed. Again Ena n? & E,# 0 as n# 0. The E,are the eigen values. From equations (6) and (7), we get we, = Asin(™) ---- (10) W, is called the eigen function.From equation 1 min = 3y (9), i ‘i ji Saar = Zero Point energy (since n= 1) E values for the particle are 1, 4, 9, 16 etc. times the minimum value. The plots of Y, & W,? against x are shown in fig (5.8) & fig (5.9) for the particle in 1-D box, From these plots it is observed that * : AS K—— x=) lta =a n=3 EE 9Ey 12 E,=4E, n=l E,= Wim % 1 ! | L x=) 5a Fa IIE SAE, pod Ey= 1S?bad | AThe probability of finding the particle (W,*) depends on x & E & is always positive. For the lowest energy state (g. s.) half wavelength covers the box & hence there is no internal node, i.e. there is no point where ,2= 0. In second energy level the wave function has one node & third has two nodes. In general, the number of nodes in the n‘* energy level = (n — 1) nodes. Greater the number of nodes more is the curvature in the wave function & greater is the total (K.E.) energyEnergy of a particle in a Three Dimensional Box Expression for energy of a particle in a one dimensional box can be extended to a three dimensional box with some modifications. Energy of a particle in a three dimensional box is given by fm? ony? na? En z(e + be + ) Where ny — Quantum number along side ‘a’ (x-axis) ny > Quantum number alon side ‘b’ (y-axis) nz, > Quantum number alon side ‘c’ (z-axis) Fig.: Particle in 3-D box Fig. $10 Parte i «3-0 box