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    QUANTUM MECHANICS __AND ATOMIC STRUCTURE _ 4.1 INTRODUCTION The idea of atomic and molecular structure (21-7 244.141) can be grasped (utes) from the study of nature of light (=/85G"..). So, first ofall we look into the various theories of light. 441.1 Corpuscular Theory Of Light: In 1675, Newton forwarded corpuscular theory of light and it was believed for more than 100 years. Anyhow, this theory was not that much applicable to explain the following phenomenons. () Polarization (ii) Diffraction (i) Reflection (iv) Refraction (v) Interference Wave theory of light appeared to be more useful at the beginning of 19th century. In order to fationalize (bt: 4 Use & ) the phenomenon of interference (iii) Vv. 2), there was no explanation in corpuscular theory. Huygens proposed the electromagnetic theory (= 4) of radiation. Maxwell also contributed (W)} <>) towards this theory. He established we 4 J) that light is an electromagnetic radiation (U*L* fs tz Gz) and is consisted of electrical and magnetic fields perpendicular (2° £ <_s £1) to each other. This theory prevailed (sz) the minds of the scientists throughout the 19th century. 41.2 Classical Theories Failed: “ From 1880 onwards a number of experimental observations (141% JL 7) were reported, which could not be explained by classical wy electromagnetic theory. These observations are as follows: i Black body radiations (i 4K LH) o pase etfect (AME ASE») (iii) Variation of heat capacities of solids with temperature (de tezwSL A phere y Seren) (iv) Atomic spectral lines discovered by Lyman and Balmer in 1887. (ZospectratBalmer stLymand- L221) Let us have a bref introduction (3-4) of Planck's quantum theory (4x2 14 SE.) which nitelv explains the above phenomenons. 157 — 158 ILMI Physical Chemistry 4.2 PLANCK'S QUANTUM THEORY 4.21 Introduction: In 1900, Max Planck studied the spectral lines (v"v 3) from the hot body radiations at various temperatures. He thought that the light radiation was produced discontinuously (< J, #3) by the molecules of the hot body. Each molecule was vibrating (UW) with the specific (6) frequency which increased with temperature. So Planck proposed a new theory that a hot body radiates energy not in a continuous way but in small units of wave. This unit wave is a pulse (4271) of energy and is called quantum. (Its plural is quanta). In 1905, Einstein showed that the light radiations emitted by excited atoms (Aixbize WL) ‘or molecules were also transmitted as particles or quanta of energy. These light quanta are called photons. Born April 23, 1856, Kiel, Duchy of Holstein Nationality German Fields Physics Institutions University of Kiel, University of Bertin, University of Géttingen, Kalser-Wilhelm- Geselischaft Alma mater Ludwig Maximilian University of Munich Known for Planck constant, Planck postulate, Planck's law of black body radiation Notable awards Nobel Prize in Physics (1918), Goethe Prize (1945) Died October 4, 1947 (aged 89) 4.2.2 Postulates Of Theory: The general quantum theory of electromagnetic radiation in the present form may be put forwarded in the following forms of postulates (1+): (i) When the atoms or molecules absorb or emit the radiation energy, then they do so in separate units of waves. These separate units of waves are called quanta or photons. It means that the “ light radiations which are obtained from excited atoms or photons are not continuous waves, but they are streams of photons (ut+7t3). Following diagram (4.1) makes the idea clear. WL OD enin waves Photon or quanta Individual Photon Fig. (4.1) Concept of generation of radiations. (ii) The energy which is associated (¢,r124) with a quantum or photon is given by the relation - quantum Mechanics and Atomic Structure : 159 a E hv Vv = Frequency of the emitted radiation h = Planck's constant having the value 6.625 x 107 erg, s = 6.625 x 10 Js If the energy is measured in ergs, then the units are erg s and when the energy is measured injoule then itis Js. (ii) An atom or a molecule can emit or absorb either one quantum of energy or any whole number multiple (ls = <-#reL) of this unit, It means that the energy associated with the radiation energy can be hv, 2hv, 3hv and so on, but never 1.7 hu, 3.9 hv etc. 42.3 Relationship Of Energy And Frequency With Wavelength And Wave Number: We know that, v| =f cian) Putting equation (2) in (1) he Th second and wavelength in meters. (1) ‘v'is the frequency of photon and it is the number of waves per second. Frequency is inversely proportional to wavelength. ~ (2) 2. = wavelength of photon in m orem. 410 m = 1A°, 10 = 1 nm, 10°%m = 14 pm| c = 2,997 x 108ms* - 8) According to equations (1) and (3), energy of the photon is directly proportional to its frequency and it is inversely proportional to the wavelength. Frequency is measured in Hertz or per t Wave number (¥) is the number of waves in one meter length so, - 4) pie ve The unit of wave number 'V' is m™' or cm”. Putting equation (4) in (2), v=cxy| : 6) Greater the wave number of the photon, greater its frequency. Putting the equation (5) in (1) E=hey 160 : LMI Physical Chemistry So, the energy of the photon is directly proportional to the wave number of the Photo The energy associated with the photon can be calculated, if we know the frequency in Hz or s, wave number in cm” or m™ and wavelength in cm™ orm”, as Two important constants i.e. velocity of light ‘c’ and the Planck's constant ‘h' should be known tous. LoLeswilP red Sa rll Guys & cine ath BEC A bal UG MELAS IIe SH trequency Suh Aujurdts Le ($5) cub utsthims\SriSe/euterg secu*hi /¢L) the number of photons incident per unit area of the surface per second. (i) For a particular metal surface the incident beam should have a minimum frequency, below which there will be no emission of electrons. This minimum frequency is threshold frequency (CF h pSASSE <7 Li) of the particular matter. (ii) If the threshold frequency is not attaifed, there will be no photoelectric current, Whatever may be the intensity of incident beam. (iv) The maximum kinetic energy of the emitted electron for a particular metal plate is Completely independent (137 z.%L) of the intensity of the beam. (v) The maximum energy of the electrons linearly depends on the frequency of the incident beam and the nature of the metal. Following Fig. (4.2) makes the idea clear. 162 ILMI Physical Chemistry Photons of fight Galvanometer Fig. (4.2) Experimental arrangement for photoelectric effect. 4.3.2 Retarding Potential: | Ifthe positive plate is made negative with respect to the plate 'P’, then the emitted electron will experience retarding potential (<7 J» x &) to reach the collector plate ‘Q’. The electron should have sufficient K.E. to overcome the retarding potential. Hence, if the retarding potential is increased gradually for a particular incident beam of certain frequency then at a certain potential, it will be found that no emitted electron will be able to reach the collector plate. This minimum required retarding potential to stop the photoelectric current is called stopping potential (=7 SLs) (Ps). Let it be noted with P, 4 7 So, 5 MV'nax = @.Ps. ‘ Vonax re eae (1) ‘Stopping potential increases in a linear manner with the increase of frequency of the beam, while it is independent of intensity of beam. Now increase the potential of the collector plate towards the positive direction with respect to the plate. The current goes on increasing. Anyhow, after a certain positive value of the potential on ‘Q', there will be no further increase of current. This Is called saturation current, The reason for this is that, all the liberated electrons having minimum or maximum velocity are able to reach the collector plate. ‘ 4.3.3 Einstein's Theory Of Photoelectric Effect: 7 In 1905, Einstein explained the photoelectric effect by the application of quantum theory of light. According to Einstein, when a photon strikes an electron, then there are two possibilities. (i). Whole of the énergy of the photon is transferred (¢stU*) to the electron: (ii) No energy of the photon is transferred. When the energy transfer takes place, then a portion of this energy will be used, to make the ‘electron free from the binding forces of metal and the residual (+t 4) energy is used to give kinetic energy to the free electron. If a electron lies below the surface €£6) ) then some additional amount of energy is also required to bring it to the surface. So, the energy of the photon will have to do three things: (i) To bring the electron to the surface. — Quantum Mechanics and Atomic Structure 163 (il) Release the electron from the surface. (iii) Giving kinetic energy to the free electron. Those electrons which are present upon the surface will need least energy under the circumstances. The electron on the surface will require minimum amount of energy to overcome the binding forces to get released. This minimum energy is called work function (w). Work function (W) =h¥o seen (2) It means that when the energy of the incident photon is less than W- or hus, then there is no emission of photoelectrons. So, J mgac+ W = hw } meat hy, = Ww 4 MV = hv—hve 5 Vn = hVv-w) sieees (8) So, ePs = Hv—v) sees (4) ‘P.'is the stopping potential. These equations (3) and (4) can explain all the observations which could not get any support {rom electromagnetic theory of radiations, 43.4 Conclusions (nh gb. 2&4) Of Einstein's Theory: i) Ifthe frequency of the incident photon ‘u'is less than threshold frequency yo'then there is no photoelectric emission, how much the intensity is greater. (i) The stopping potential 'Ps'is independent of the intensity ofthe photon. This aspect (o¢) % was veriied by Milikan experimentally. ; Equation (4) can be modified, ‘ hv hye a po vm sesseen ? This is equation ofa straight ine and if graph is plotted between frequency ‘v' on x-axis and 'Pi'on y-axis, a straight line is obtained as shownin the following diagram (4.3). ~ (eget Lt 6b gp £7 se _le-eThreshold ) 164 ILMI Physical Chemist > - be calculated. Fig. (4.3) Variation of stopping voltage for the emitted photoelectrons with frequency of incident radiation. The intercept of the straight line gives value of (), so the threshold frequency v, can 'Y ve is known, then the value of the Planck's constant 'h’ can be calculated. Itwas Millikan who determined the value of Planck's constant bby using this equation and the result was in agreement with Values from other sources. This verification gives a ‘Support to the validity (tse) of Einstein's equation (3), (4) and (5). Institutions Alma mater Known for Notable awards Died 14 Match 1879, Ulm, Kingdom of Wirttemberg, German Empire Germany, Italy, Switzerland, Austria, Belgium, United States Kingdom of Warttemberg (1879-1896), Stateless (1896-1901), Switzertand (1901~1955), Austia-Hungary (1911-1912), German Empire (1914-1918), Weimer Republic (1919-March 1933), United States (1940-1955) Physics Swiss Patent Office (Bern), University of Zurich, Charles University in Prague, ETH Zurich, Caltech, Prussian Academy of : Sciences, Kaiser Wilhelm Institute, University Albert Einstein of Leiden, Institute for Advanced Study. ETH Zurich, University of Zurich General relativity and special relativity, Photoelectric effect, Mass-energy equivalence, ‘Theory of Brownian Motion, Einstein field equations, Bose-Einstein statistics, Bose- Einstein condensate, Bose-Einstein correlations, Unified Field Theory, EPR paradox Nobel Prize in Physics (1921), Matteucci Medal (1921), Copley Medal (1925), Max Planck Medal (1928), Time Person of the Century (1999) 18 April 1955 (aged 76) ‘ , 165 quantum Mechanics and Atomic Structure 4.4 COMPTON EFFECT 4dd Introduction: : When a beam of light which is consisted (tx J%) of X-rays having sharply defined frequencies strikes a material, then it is scattered (¢-Ge_). The material should be of low atomic ruber (i717) in which the electrons are loosely bonded to the parent atom. The scattered light Gude 6A) undergoes change of frequency and wavelength (Jt/ ). The wavelength of the scattered light is increased (<-Jy oxS A ‘15.164. This change of wavelength depends upon the scattering angle (_s176e 1A) and does not depend upon the wavelength of the incident beam. The scattered beam is often associated with the unchanged wavelength, along with the new longer wavelength. This phenomenon is called Compton effect because A.H. Compton discovered it in 1923. 442 Compton's Explanation (6 2 Uvi##): This phenomenon is explained by him on the basis of quantum theory (14, ). According to which light is consisted of photons of energy hv. According to the theory of relativity (231+ /P) mass and energy are equivalent. So, photons having energies can be considered as particles of definite mass (e's). It means that when a photon hits the material particle say electron, then the collision can be thought of as elastic between the photon and the electron. When the photon of energy hy strikes on electron, it will transfer some of its energy as kinetic energy to the electron. So, the energy of the photon become less. The scattered photons will have longer wavelengths, smaller frequencies and smaller energies. ” (ager Kt euf suis ilove ne Aletnplivetiasr Lyf Peon 44.3 Mathematical Background Of Compton Effect: Compton has considered the following aspects (s4¢) and gave a sound theoretical basis to this effect, () Quantum theory (6/4). (ii) Principle of relativity (U-i¥=dl1). (ji) Law of conservation of momentum (27 14-2 wy6), (iv) Law of conservation of energy (Sti7Ztw96). Let us suppose that the frequency of the photon before collision = y Frequency of the photon after collision = Vv Loss in energy of photon SVAN (1) Energy of photon (e) = Pxe . ” [Because = me? = mc.¢ = Pc Where, P = Momentum of photon © = Velocity of light be ILMI Physical Chemistry : 2) So, the momentum of the photon is i ‘According to the principle of conservation of momentum es Ae ee oan (©/7 Aw) of each particle should be ‘conserved in two mutually perpendicular directions (. wo a . . Look al the following diagram (4.4) in which the scattering angle for the photon is ‘' and that ; for the electron is ‘6’. These two angles are to the direction of the incident photon. incident pon € =, P= Recoil electron Target clectron atrest Comet P! =Momentum of electron Fig. (4.4) Compton effect, scattering of photon and electron due to collision Energy of target electron = mec? Momentum of electron before collision = 0 Let us consider the momentum along the incident direction and so we can write, eM ewe ieee ISIS hore tryst tw tw c tO FG COSHHPIXCOSA tse @) Where Momentum of electron after scattering = Momentum of electron before scattering = Momentum of photon before scattering ——x cos = Momentum of photon after scattering. Now consider the momentum in the perpendicular direction, (7 beberwor') hv a 0 = “e sing - Pr. sin ® sisson (4) quantum, Mechanics and Atomic Structure 167 hv Where, “_ sin = Momentum of photon after scattering in perpendicular direction P’.sin@ = Momentum of the electron after scattering in perpendicular direction. According to equation (4), the momentum of the photon and electron in perpendicular directions are zero. When we join equation (3) and (4), we get following two equations P’.c.cos® = hv—hv’.cos> - © Pic.sin@ = hv.sing + (6) If we handle equation (5) and (6) in such a way that we eliminate the angle @, which is the scattering angle of electron, then we have to take the squares of the equation (5) and (6), add them together and get the following relationship. Price = (hyP+(hv)?—2(hy) (hv) cos ee (7) The energy (F) of the particle, which has been scattered after hitting with photon is, Es Teme 2 2.2. 2... cme (8) T = hv—hy = Amount of energy lost by photon a 9) Equating equation (8) and (9), Niece! + pc? = T + mec? motel + pc? = T+ mec +2 T mec? P2 cl = T2+2mc2.T tee (10) ‘We know that, T = hv-hv Putting this value of T'in equation (10), we get Po? = (hy?+ (hv’)2— 2(hy) (hv!) +2mec2(hy— hi’) sss (11) Let us combine the equation (7) and (11) 2mee? (hv— hv) = (hy) (hv’) (1 —cos 4) Dividing this equation with ‘he’ me (ex) = ¥ x 1-009) hee c 5a (f 4) 2 tecsd han aN Rearranging above equations, h N-M = mee (1-008 4) (12) The equation (12) is a very useful equation, and gives some important results. It describes the Compton effect quantitatively. 2! = Wavelength of scattered photon 2. = Wavelength of incident photon ™, = Rest mass of electron = Scattering angle of photon a’ 168 ILMI Physical Chemistry h ne = Compton wavelength of the scattered particle Since, 1—cos p = 2 sin? (4) So, equation (12) can be written as follows: vm (9) AX is called Compton shift. It is the independent of the incident radiation and nature of the ‘scattering material. It depends upon the scattering angle. Mu Geneve Aspne ty ngrsud (dS zum xSCompton Effect se Ff Se BL So SME nl SaaS (13) When o 0 cos = 4 h waa = Te t-1) N-w = 0 lf means that there is no scatterin When > = 180° cos 180° = -1 1g and no change of wavelength for the incident photon. h Moa = TE +4) ' - 2h Noa = Ao De (te us see that a = 24) Equation (14) tells us that there is maximum Scattering at this angle. When 8 = 90° cos 90° = 0 see (14) NAR = h NaReT EA + (18) If we use the standard values of h, m and c then the value of the Compton wavelength, =n is 0.024 A®. It means this is the wavelength change which can take place when the ‘scattering angel is 90°. can vary from 0° to 180°. The wavelength of scattered photon can vary from 2. to 0+ 2r¢. It means that the maximum wavelength shifts may occur by 0.048 A°, These small changes can be only noted for the X-rays, whose wavelengths are in the order of 1A°. If we use the visible light for this purpose, then the wavelength shift is very very small. | quantum Mechanics and Atomic Structure 169 4.5 BOHR'S MODEL OF ATOM 45.1 Introductior Bohr, a Danish Physicist, put forward his atomic theory in 1913. With the help of this theory, he was able to account for (&»—L>) the existence of line spectra Gx LiF HA). The justification Ww fet ) of line spectra was a buming question of that time. He also gave the support to the fact that the atoms should not collapse. Actually he modified Rutherford's model, with the help of quantum theory of radiations which was proposed by Max Planck in 1900. Bohr’s model is for hydrogen atom and can also be applied to study the line spectra of He®, Li© ete. which are monoelectronic systems. 45.2 Postulates of bohr’s Model: (The electron revolves around the nucleus ina circular orbit (Js), These orbits are fixed. (i) When the electron remains in the same orbit it neither loses energy nor gains energy. These non-radiating orbits are called stationary states wr bob). (iii) The electron can lose or gain the energy when it changes the orbit. (iv) Energy which is emitted or absorbed is in the form of quantas or small packets ®. The energy difference between any two orbits is given by the formula AE = hv . Where vis the frequency of the photon, (v) Since energy can not be lost continuously (4 L713), so an electron continues (4 Gx) to move in a particular energy level (4J23.A%6) without losing energy. This state of atom is known as normal or ground state. When the electron goes to a higher orbits by absorbing:a photon, then it is called excited state (Soden. (vi) Only those orbits are permitted (ee! EAT of J) in which the angular h 2n° momentum (<7 A«-Jis4) ‘mur is the whole number multiple of -ah mur = 97 It means that the position of the orbit (Lz ur4J7) is quantized (ext W). The electron A move i aos h 2h 3h ; will move in the orbits having mvr as Qn! On' On 7777"s8tC. Electron is not allowed to move having angular momentum in between these values. WP ne Bet NP ELLE 0 LF7 JebesineE yo 61) 7 (utquantized ATL py Sets | 453 _ Difference Between Bohr’s Model And Rutherford's Model: 1) Bohr believes in the quantization of energy and quantization of angular momentum of electron. i The quantization mean that a quantity can Vary only discontinuously to get a specific { ee Rutherford had no idea of quantization, Rutherford's model could not explain series of i : —_—§., 170 ILMI Physical Chenilstry (2) The spectra of the hydrogen which was recorded before Bohr's theory got its justification from the stationary states and the idea of quantization. 4.5.4 Mathematical Equation For Radii Of Bohr's Model: Keeping in view the revolution of electron of hydrogen atom in the ground state and its possibility to be promoted to higher states, compells us to equate the centripetal force and the force of attractions. In this way, we get the value for the radii of various orbits of hydrogen atom. The final expression for radius of orbit having Z protons in the nucleus of an atom is Thee ° ey (1) where h Planck's constant= 6.25 x 10™ Js u 3.414 m = Massofelectron = 9.1 x 10kg Z = Number of protons in the nucleus. e Charge ofelectron = 1.602 x 10%c i Permitivity constant of medium = 8.854 x 1072 71m n = Number of orbit When we substitute the values of all these constants for hydrogen atom (Z = 1), then 529 A® (7) Q) : By putting the values of n= 1, 2, 3, 4, --+--- ete. the radii of different orbits of hydrogen atom are as follows: 1, = 0529A°(1)? = 0.529 A° fy = O529A°(22 = 24142 fy = O529A°(3)2 = 484° ry = O529A° (4)? = 84A° fs = 0529A°(5)2 = 13.2A° It means that the second orbit is four times at a greater'distance than the first orbit. Second orbit is nine times away, fourth orbit is sixteen times away and fifth orbit is twenty five times away. In other words the atom becomes more and more thin by keeping in view the distances of the orbits among themselves. 455 Expression For Energy: When we sum up the kinetic and potential energy of the moving electron around the nucleus then our final expression is, by vl aLe tlw A Li Lite vel hiya sa Se pet eel are 2 Vz EE If we put the values of constants for hydrogen atom, then aa quantum Mechanics and Atomic Structure 171 So, &2-218x 10. (4) A berecereeenesetsccst (4) 456 Significance Of Negative Sign: ‘ The significance ( Ans, 479 Relativistic Correction € Pi gLedlilyS): / ifthe potential difference applied is very high, then the velocity of electron becomes very high and the wavelength of the electron becomes very small. Under these conditions the mass of electron increases according to theory of relativity. So, we should compare the moving mass of the electron with the stationary electron i.e. Mi oe Ifwe substitute this value, in equation (9), then it changes to oi ae [r+ 2] Rep seeee (10) 4.8 HEISENBERG'S UNCERTAINITY PRINCIPLE (Urreg S60 L204) 484 Introduction: When we are studying a large moving object say a planet, then we can follow its definite path on which it travels. If we know its initial position and momentum, then we can predict its position and ‘momentum at any other time. But this is not possible for electron, proton and neutron which are microscopic particles. Heisenberg has given a principle in this connection. He says that it is impossible to measure simultaneously both the position and momentum of a microscopic Particle with accuracy or certainity. Mathematically this principle can be put as follows: mn rw h AX x AP 2a AX = Uncertainity in the position AP = Uncertainity in the momentum Tiros These two uncertainities are inversely proportional to each other, So, if position of the ‘oe Particle is known with more accuracy, then there will be more uncertainity in its momentum versa, 482 Physical Concept Of Uncertainity Principle (Siig? 322-1): |n order to know the position of an object, we throw the photons of light upon them. If we want the idea for the position of electron, then the photons of X-rays region have to be used because fengths are very small and the possibility for the hitting of electron is there. During this hitting, or have 188 ILMI Physical Chemistry the photon transfers (+ /. F) some of its energy to the electron. Therefore, the velocity and hence the momentum of electron changes. If we use the photons of longer wavelength say of visible region, the velocity and the momentum will not change appreciably (£4 *t 4) because longer wavelengths rarely find the chance to hit the electron. But its position can not be determined because object will not be visible. Keep itn mind that, the uncertainty is not due to lack (if) of better techniques (62.7) for the measurement of position and momentum, It Is due to the reason that we cannot observe the microscopic objects without disturbing them. Uncertainity principle is not applicable to stationary electron (ut, 6 Sf ‘L-) because in stationary state the velocity of an electron is zero. As a result, position of electron can be accurately determined. But both positions and velocities of electron cannot be determined accurately. 4.8.3 Mathematical Form Of Uncertainity Principle: We have to consider an hypothetical (.s* 7) experiment in which we'can measure the position and velocity of an electron. Following diagram (4.14) shows an arrangement in this respect. | scattered hy'= scattered light ~ light photon of E= hy x Y Fig. (4.14) Microscope to study the uncertainity principle. A photon from a source of y-rays or X-rays with energy ‘hu’ strikes the electron at the point P. When the electron scatters (— aA this photon into the microscope in a direction making an angle 'B’ with the x-axis, the electron will receive some momentum (<7 sl+-), from the photon along x-axis. Scattered photon can enter the microscope anywhere within the angle ‘2c’. Its contribution (Au) t0 x-component of the momentum of electron is, AP, = 2P sin 4 SiN tees (1) av (secause ae *) > 189 tun Mechanics and Atomic Structure_* — Rayleigh's equation for the resolving power (. GLI busi) can be used to find the y! ccuracy (eG )with which an object can be located (¢/7 pf) by a microscope and is given by, AX ‘AX = Distnace between two points which can just be resolved (tc ee ) by the microscope 2 = Wavelength of photon Multiplying equation (1) with (2), dR 2h AX. AP. = Fein, Sa wh (3) According to the equation (3), the product of two uncertainities lies in the range of the calculation is done more carefully, then we come to know that, ‘hs If h AX. APx2 47 cee (4) This equation indicates that greater the accuracy in determining the position, greater the uncertanity in determining the momentum, Thus a certainity in one quantity introduces an uncertainity inits conjugate (21417) quantity. In other words, if one quantity is known free from error, then the error in the other quantity becomes infinity. When AX = 0 h AP = Fax AX * 48.4 Uncertainity Of Velocity: ‘According to the definition of momentum (©/7 A), and.change of momentum, AP = mx Av : Itmeans that, h AXxmx AV 2 Ar h Av x AX2 40m So, itis difficult to determine the velocity and position of electron simultaneously. eH LSM LSA NB Uncertainity principle can also be applied for another conjugate pair i.e. energy and time. Since, 1 av = i As, AE = hx Av a So, AE = at AE x At = h nn 190 ILMI Physical Chemistry More realistic treatment shows that, h AE x At = On It means that it is simultaneously. ifficult to determine the energy and time for the Particle So, Heisenberg uncertainity principle is applicable to any y conjugate pairs (2 Juin) of variables (2 yt) and we reach the Conclusion that the product of ncertainities of any two Conjugate P ‘tht Variable is always constant and its Value range between On and ie Wemer Karl Heisenberg, 5 December 1901, Wirzburg, Bavaria, Germany Died 1 February 1976 (aged 74) Nationality German Fields Theoretical Physics Institutions University of Gottingen, University of Copenhagen, University of Leipzig, University of Betin, University of Munich Alma mater University of Munich Notable awards Nobel Prize in Physic (1932), Max Planck Medal (1933) 48.5 Uncertainity Principle And Particles Of Different Sizes: () Consider the motion of electron in hydrogen atom, Suppose that the position of electron from the nucleus can be determined with a uncertainity (7 < &) of 4 pmie. 4 x 107? m. This Means that the revolving electron Aine dS, uz) may lie in first Bohr’s orbit having the radius in the range of 53 + 4, (53 pm is the radius of first Bohr’s orbit). The Corresponding uncertainity in defining the velocity will be, = tL © 2nmaxX 6.625 x 10° Js Ave Fx atx 81x 10% kg x 4x 102 = 2.9% 107m. secct This is the uncertainity of the velocity, in Bohrs first orbit. The velocity of electron in the first Bohr's orbit comes out to 2.2 x 106 m. sect. The value of Av is much large than the velocity of electron. It means that the trajectory (>u¥i_/. =/7) of the electron can not be defined. In other words Bohr’s orbits become meaningless (_ 5” J/¥7) inthe light of uncertainity principle. . (i) Let us consider a ball of mass 2-9, having an Uncertainity in its position AX as 107 m. The uncertainity in its velocity will be h 2nm AX Av = : | quantum Mechanics and Atomic Structure 191 — ay = 6.625 x 10 Js 2x 3.1416 x 2 x 103k x 10m = 0.525 x 10 m sect This uncertainity of velocity is negligible as compared to the velocity of a bali. Hence, the both velocity and position of macroscopic particle can be determined precisely. 4.86 Applications Of Uncertainity Principle: () Electron can not exist in the nucleus (FuudaLus*eoi7An: We know that the radius of the nucleus of the atom is in the range of 10° m. For an electron to remain within the nucleus, the ‘AX' must be 10™ m. Knowing the value of 'AX’, the value of 'Av' will be calculated as follows: > * 4m aX av 2 6.625 x 10° kg. m?. sect 4 x 3.142 x 9.108 x 10° kg x 10° m Av 2 5.77 x10? ms". . This value of Av is greater than the velocity of light ie. 3 x 10" m sec"*. So an electron cannot exist in the nucleus. (i) Probability Concept of Electronic Cloud: We can never locate the exact position around the nucleus for the revolving electron. Av ‘Sample Problem (4.7) The uncertainty in the momentum of a particle is 3.5 x 10 kg ms". Calculate the uncertainty in its position. Solution: Uncertainty in momentum, AP = 3.5 x 10 kg ms" h = 6.625 x 10° Js = 6.625 x 10° kg m?s ‘According to Hesienberg's uncertainty principle, h Axx AP = in fh Ax 2 Ipx4n Putting values 6.625 x 10™ kg m? st AX 2 35x 107kgms' x 4x 3.14 Ax > 0.1507 x 10m = [4.507 x10 nm] Ans, 4.9 OPERATORS An operator (ut ’ irs) is a mathematical instruction (=<14) or a procedure (2 A¥L4) ‘obe cartied out on a function so as to get another function. > ——————==s 192 LMI Physical Chemistry Operator is written on the L. the function to get another function. When an operator is written alone, it has no significance. The function on which the operator is carried out is called operand. Function Pore inbalt sree HOI us adele Examples: (i) When we take a square root (4) of a quantity, then we give instruction to that quantity, So that if the answeris multiplied itself au, P= Te), we get the original quantity, V8 = 4% Similarly, to take the cube root is another operation, (i) Another important example of mathematical operation is the differentiation ( £65 212, The symbol Sis an operator Which instructs that the function should be yt aX pel differentiated with Tespect tox’, 4 (8) = 3x2 (il) Muttiplication is also an operation So, XX = we Operators may occur in combinations. For example, x & + Means that the function should be differentiated first of all with respect fo 'X’ and then multiplied by "x’, qd X. GX 00) = Xx) = 3x0 When we have combined operations, then the operators are used starting with the right hand one. 4.9.1 Linear Operator: When we have the summation of @ few functions, then the differential operator can differentiate them separately. So differential Operator is a linear operator. d d & (X64 3x) = aX Xt) + ay XQ) = 4X3+6X d doy _ _— ax (9X) = Sax 08) = 5x 3X2 = 15x The operator YI "is not linear operator. V16+25 # V6 + 25 4.9.2 Addition And Subtraction Of Operators: Suppose K and B are two different operators and 'X' is operand (

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