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Quantum Mechanics WAVES A wave is nothing but disturbance which is occurred in a medium and it is specified by its frequency, wavelength, phase, amplitude and intensity. PARTICLES A particle or matter has mass and it is located at a some definite point and it is specified by its mass, velocity, momentum and energy. • The physical values or motion of a macroscopic particles can be observed directly. Classical mechanics can be applied to explain that motion. • But when we consider the motion of Microscopic particles such as electrons, protons……etc., classical mechanics fails to explain that motion. • Quantum mechanics deals with motion microscopic particles or quantum particles. of de Broglie hypothesis • In 1924 the scientist named de Broglie introduced electromagnetic waves behaves like particles, and the particles like electrons behave like waves called matter waves. • He derived an expression for the wavelength of matter waves on the analogy of radiation. • According to Planck’s radiation law E h c h ............(1) • Where ‘c’ is a velocity of light and ‘λ‘is a wave length. • According to Einstein mass-energy relation E mc2 ......(2) mc h 2 From 1 & 2 c h mc h p Where p is momentum of a photon. • The above relation is called de Broglie’ s matter wave equation. This equation is applicable to all atomic particles. • If E is kinetic energy of a particle • Hence the de Broglie’s wave length 1 E mv 2 2 p2 E 2m p 2 mE h 2mE de Broglie electrons wavelength associated with Let us consider the case of an electron of rest mass m0 and charge ‘ e ‘ being accelerated by a potential V volts. If ‘v ‘ is the velocity attained by the electron due to acceleration The de Broglie wavelength h m0 v 0 12.26 A V h 2eV m0 m0 1 m0 v 2 eV 2 2eV v m0 Characteristics of Matter waves • Lighter the particle, greater is the wavelength associated with it. • Lesser the velocity of the particle, longer the wavelength associated with it. • For V= 0, λ=∞ . This means that only with moving particle matter wave is associated. • Whether the particle is charged or not, matter wave is associated with it. This reveals that these waves are not electromagnetic but a new kind of waves . It can be proved that the matter waves travel faster than light. E h We know that E mc2 mc2 h mc h 2 The wave velocity (ω) is given by w mc2 h w( )( ) h mv 2 mc h As the particle velocity v cannot where & h mv exceed velocity of light c, ω is greater than velocity of light. c2 w v Experimental evidence for matter waves 1.Davisson and Germer ’s Experiment. 2.G.P. Thomson Experiment. DAVISON & GERMER’S EXPERMENT • Davison and Germer first detected electron waves in 1927. • They have also measured de Broglie wave lengths of slow electrons by using diffraction methods. Principle: • Based on the concept of wave nature of matter fast moving electrons behave like waves. Hence accelerated electron beam can be used for diffraction studies in crystals. Experimental arrangement • The electron gun G produces a fine beam of electrons. • It consists of a heated filament F, which emits electrons due to thermo ionic emission • The accelerated electron beam of electrons are incident on a nickel plate, called target T. The target crystal can be rotated about an axis perpendicular to the direction of incident electron beam. • The distribution of electrons is measured by using a detector called faraday cylinder c and which is moving along a graduated circular scale S. • A sensitive galvanometer connected to the detector. High voltage Nickel Target Anode filament cathode G Faraday cylinder c S Circular scale Galvanometer G Results • When an electron beam accelerated by 54 volts was directed to strike the nickel crystal, a sharp maximum in the electron distribution occurred at scattered angle of 500 with the incident beam. • For that scattered beam of electrons the diffracted angle becomes 650 . • For a nickel crystal the inter planer separation is d = 0.091nm. Incident electron beam 0 650 25 250 650 I V = 54v C U R R E N T 0 500 θ Diffracte d beam • According to Bragg’s law 2d sin n 2 0.091nm sin 650 1 0.165nm • For a 54 volts , the de Broglie wave length associated with the electron is given by • This is in excellent agreement with the experimental value. • The Davison - Germer experiment provides a direct verification of de Broglie hypothesis of the wave nature of moving particle. 0 12.26 A V 0 12.26 A 54 0.166nm G.P THOMSON’S EXPERIMENT • G.P Thomson's experiment proved that the diffraction pattern observed was due to electrons but not due to electromagnetic radiation produced by the fast moving charged particles. EXPERIMENTAL ARRANGEMENT • G.P Thomson experimental arrangement consists of (a) Filament or cathode C (b) Gold foil or gold plate (c) Photographic plate (d) Anode A. • The whole apparatus is kept highly evacuated discharge tube. • When we apply potential to cathode, the electrons are emitted and those are further accelerated by anode. • When these electrons incident on a gold foil, those are diffracted, and resulting diffraction pattern getting on photographic film. • After developing the photographic plate a symmetrical pattern consisting of concentric rings about a central spot is obtained. G.P THOMSON EXPERIMENT cathode Discharge tube slit Anode Vacuum pump Gold foil Photo graphic plate Photographic film Diffraction pattern. E Incident electron beam A θ Brage plane r Gold foil B radius θ θ L Tan 2θ = r / L If θ is very small 2θ = r / L 2θ = r / L ………. (1) o c 2d sin n ( and , n 1) 2d ( ) n L d d d r 2 r ( ) L According to de Broglie’ s wave h equation 2m0eV According to Braggs law m0 m v2 1 2 c Where m0 is a relativistic mass of an electron n from., eq (3) L L h d d ( ) r r 2m0 eV d 4.08 A 0 • The value of ‘d’ so obtained agreed well with the values using X-ray techniques. • In the case of gold foil the values of “d” obtained by the x-ray diffraction method is 4.060A. Heisenberg uncertainty principle • This principle states that the product of uncertainties in determining the both position and momentum of particle is approximately equal to h / 4Π. h xp 4 Where Δx is the uncertainty in determine the position and Δp is the uncertainty in determining momentum. • This relation shows that it is impossible to determine simultaneously both the position and momentum of the particle accurately. • This relation is universal and holds for all canonically conjugate physical quantities like 1. Angular momentum & angle 2. Time & energy h 4 h t E 4 j Consequences of uncertainty principle • Explanation for absence of electrons in the nucleus. • Existence of protons and neutrons inside nucleus. • Uncertainty in the frequency of light emitted by an atom. • Energy of an electron in an atom. Physical significance of the wave function • The wave function ‘Ψ’ has no direct physical meaning. It is a complex quantity representing the variation of a Matter wave. • The wave function Ψ( r, t ) describes the position of a particle with respect to time. • It can be considered as ‘probability amplitude’ since it is used to find the location of the particle. ΨΨ* or ׀Ψ׀2 is the probability density function. ΨΨ* dx dy dz gives the probability of finding the electron in the region of space between x and x + dx, y and y + dy, z and z + dz. * dxdydz 1 - 2 dxdydz 1 - The above relation shows that’s a ‘normalization condition’ of particle. Schrödinger time independent wave equation • Schrödinger wave equation is a basic principle of a fundamental Quantum mechanics. • Consider a particle of mass ‘m’ ,moving with velocity ‘v’ and wavelength ‘λ’. According to de Broglie, h p h ...........(1) mv • According to classical physics, the displacement for a moving wave along X-direction is given by S A sin( 2 x) • Where ‘A’ is a amplitude ‘x’ is a position co-ordinate and ‘λ’ is a wave length. • The displacement of de Broglie wave associated with a moving particle along X-direction is given by (r , t ) A sin( 2 x) If ‘E’ is total energy of the system E P.E K .E h ( )2 p2 E V V 2m 2m 2 h E V 2m2 h2 E V ......(2) 2 2 m Periodic changes in ‘Ψ’ are responsible for the wave nature of a moving particle d ( ) d 2 [ A sin .x ] dx dx d ( ) 2 2 A cos( .x) dx d 2 2 2 2 [ ] A sin( .x ) 2 dx d 2 4 2 2 2 A sin( .x ) 2 dx d 2 4 2 2 2 dx 1 1 d 2 2 (3) 2 2 4 dx From equation 3…… h2 E V 2 2m h2 1 d 2 [ ] [E V ] 2 2 2m 4 dx h 2 d 2 [E V ] 2 2 8 m dx d 2 8 2 m [ E V ] 2 2 dx h d 2 8 2 m [ E V ] 0 2 2 dx h This is Schrödinger time independent wave equation in one dimension. In three dimensional way it becomes….. 2 2 2 8 2 m 2 2 2 [ E V ] 0 2 x y z h Particle in a one dimensional potential box • Consider an electron of mass ‘m’ in an infinitely deep one- dimensional potential box with a width of a ‘ L’ units in which potential is constant and zero. v ( x ) 0,0 x L v ( x ) , x 0 & x L V=0 X=0 X=L V Periodic positive ion cores Inside metallic crystals. V + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + X One dimensional periodic potential in crystal. The motion of the electron in one dimensional box can be described by the Schrödinger's equation. d 2 2m 2 [ E V ] 0 2 dx Inside the box the potential V =0 d 2 2m 2 [ E ] 0 2 dx d 2 2m 2 2 k 0 where, , k 2 E 2 dx The solution to above equation can be written as ( x) A sin kx B cos kx Where A,B and K are unknown constants and to calculate them, it is necessary to apply boundary conditions. • When X = 0 then Ψ = 0 i.e. |Ψ|2 = 0 ……. a X=L Ψ = 0 i.e. |Ψ|2 = 0 …… b • Applying boundary condition ( a ) to equation ( 1 ) A Sin K(0) + B Cos K(0) = 0 • Substitute B value equation (1) Ψ(x) = A Sin Kx B=0 Applying second boundary condition for equation (1) 0 A sin kL (0) cos kL A sin kL 0 sin kL 0 kL n k n L Substitute B & K value in equation (1) (nx) ( x) A sin L To calculate unknown constant A, consider normalization condition. L Normalization condition ( x) 2 dx 1 0 nx o A sin [ L ]dx 1 L 2 2 1 2nx A [1 cos[ ]dx 1 2 L o L 2 A2 L 2nx L [x sin ]0 1 2 2n L A2 L 1 2 A 2/ L The normalized wave function is n n 2 / L sin x L 2mE k 2 2 2 k E 2 2m n h L 2 E 2m n h where,.k & L 2 n2h2 E 8mL2 2 2 The wave functions Ψn and the corresponding energies En which are called Eigen functions and Eigen values, of the quantum particle. Normalized Wave function in three dimensions is given by n3z n1x n2y n (2 / L ) sin sin sin L L L 3 The particle Wave functions & their energy Eigen values in a one dimensional square well potential are shown in figure. nx n 2 / L sin L n2h2 En 8mL2 E3=9h2 / 8mL2 n =3 L/3 2L / 3 E2=4h2/8mL2 n=2 L/2 √ (2 / L) E1=h2 / 8mL2 n=1 X=0 L/2 X=L Conclusions 1.The three integers n1,n2 and n3 called Quantum numbers are required to specify completely each energy state. 2.The energy ‘ E ’ depends on the sum of the squares of the quantum numbers n1,n2 and n3 but not on their individual values. 3.Several combinations of the three quantum numbers may give different wave functions, but not of the same energy value. Such states and energy levels are said to be degenerate.