ee Chapter 1 Quantum Mechanics and Atomic Structure ———————— ee INTRODUCTION One of the early attempts to understand the structure of atom was put forth by Rutherford in 1911. In Rutherford’s nuclear model of the atom, negatively charged electrons revolve around the central positive nucleus of the atom, The entire mass of the atom is concentrated in the nucleus. ‘A major setback of this model of the atom was its stability. The electron (electrically charged particle) in motion around the nucleus would continuously lose energy by emitting radiation. This will resuit in the orbit becoming smaller and smaller and finally falling into nucleus. This does not happen and the model was not acceptable. 1.1 BOHR’S ATOMIC MODEL Niels Bohr, a Danish physicist improved this model of the atom. The concept of the nucleus proposed by Rutherford was retaized but the quantum theory of radiation putforth by Max Plank was applied. This model could explain the line spectrum of the hydrogen atom. Postulates of Bohr's Model 1. The electron in an atom revolves round the nuctzus (small, central core of the atom) in definite closed circuits called the orbits. 2. The orbits are at a fixed distance from the nucleus. Each orbit is associated with a definite amount of energy. 3. The angular momentum ofthe electron is quantised such that itis an integral multiple of h/2n where h is Plank’s constant. [Angular momentum mvr=nh/2x where m is the mass, vis the velocity of the electron and r is the radius of the orbit. n is any integer] 4. follows from the above postulates that only orbits of certain radii and having ceriain energies are allowed. These are called ‘stationary orbits’ or ‘stationary states’, 5, As long as the electron is in one of these orbits, it does not radiate any energy. 6. The farther the energy level from the nucleus, the greater isthe energy associated with it, When radiant energy is present, the atom may absorb energy. ‘This results in the electron jumping from a stationary obit of lower energy (inner orbit) to another of higher energy (outer ori) The frequency 0 ofthe radiant energy corresponds to the ‘ee AB hetween the two stationary orbits, ie., 3 energy differen Scanned with CamScannert : College Chemistry - I] Similarly, when the electron jumps from an orbit of higher energy (outer) to one of lower energy (inner orbit), excess energy AE is emitted as radiation of frequency v. Energy is neither absorbed nor emitted gradually but in units of quantum, hv where h is Plank’s constant and v is the frequency of the radiant energy. The above postulates appeared quite arbitrary at the time they were proposed but . subsequently proved to be reasonably valid from wave mechanical considerations. Bohr's theory thus, could explain the line spectrum of hydrogen and also predict all the spectral lines of the hydrogen atom. , Scanned with CamScanner. 1.4 HYDROGEN SPECTRUM AND ENERGY LEVEL DIAGRAM The hydrogen atom contains only one electron. According to Bohr’s original theory the energy levels of the hydrogen atom correspond to a-series of circular. electron orbits. The spectral lines are produced when the long electron in hydrogen atom transits from one energy level to another. Energy is emitted when an electron moves from an orbit of quantum number, n, (higher energy level) to another orbit of quantum number n, (lower energy level). Energy is absorbed if the electron moves in theropposite direction Le., from n, ton. The orbit of quantum number n, i.e., a = | in the hydrogen atom is called the normal orbit ane eround state. It represents the stationary state of the unexcited atom. Energy may be oe eis discrete quantities, to an electron by thermal agitation or by collision with another ina results in exciting the electron i.e., the electron moves into a higher energy level particle. FDIS Scanned with CamScanner/ College Chemistry 11 from n= 1 energy level. In this new level, the electron aa eae aes stable. It falls back to ground level (n = 1) either in single step or ina aumer of lermediate steps. During the process of this transition the electron loses energy and the loss in energy is radiated as a photon of frequency v. In the orbit n = 1, the energy of the electron is the most negative. This is the most stable orbit and refers to the lowest energy level of an atum. Orbits where n= 2, 3, 4, .... are called the excited states as the energy of the electron in these orbits are higher. The radius of cach orbit varies as n” so that as the value of n increases, the size of the orbit increases rapidly and are farther away from the nucleus. Figure 1.4 gives a graphical representation of the energy levels in the hydrogen atom and the various emission series. _— é T Ss : l I Brackett 3 series 5 Paschen a series ; Hl r 2 aI Balmer y| series n=1— Lyman series Fig. 1.2 : Energy levels in the hydrogen atom and the various emission series Spectral lines are produced by the radiation of photons. When the emitted radi: examined by means of a spectroscope, a series of well defined sharp lines are observed. Each line corresponds to a definite wavelength or frequency. Line spectra are characteristic of atoms. lation is ‘The Balmer series of spectral lines were the first to be discovered. 4 | In 18: showed that the wave number of any spectral line in the visible re Soe palmer governed by the empirical formula 1 R |. -- «leis where n has values 3, 4, 5, ... and R is an empirical constant ca gion of hydrogen atom is led the Rydberg constant. Scanned with CamScannerMechanics and Atomic Structure in Quantum J 9 Bohr was able to exactly reproduce Balmer’s formula from his energy expressioy , atecron in atom, He wa also able co predict al the lines in the specteum of atomic hyde including those in the infrared and ultraviolet regions, drogen | Hydrogen contains only one electron and its spectrum isthe simplest to analyse, Each in the emission spectrum of hydrogen corresponds to a particular electronic transition, The» vision spectrum covers a wide range of wavelengths from the ultraviolet to the infareg, Different series of spectral Lines are seen arising due to different inner orbits t0 which the electron falls, The series are named after their discoverers. Table 1.1 gives the series of transitions and the spectral region in which they are observed. Table 1.1: Spectral Series in Atomic Hydrogen Emission Spectrum ai Series "nat Mas Spectrum region } I I | Lyman 1 23,4 Ultraviolet Balmer 2 3.4, Visiblefultraviolet Paschen 3 4,5, Infrared | Brackett 4 5, 6, Infrared | Pfund : 6. 7, 8.. Infrared ) 1.4.1 Ritz Combination Principle The equation obtained by Bohr for the wave number of the spectral line in the spectrum of atomic hydrogen is identical with the general equation put forth for the wave number of any spectral line within the spectral series of a given atom or ion by W. Ritz in 1908. According to Ritz, the wave number of any spectral line may be represented as a combination of two terms, one of which is a constant and the cther a variable throughout each spectral serics. The general formula of Ritz combination principle was given as | | . 7 } where x is a constant term. The values of x and y are integers for hydrogen but not necessarily 0 for other atoms, Ritz combination principle is applicable for the entire range of spectroscopit investigation, Bohr’s theory could give = theoretical support to Ritz combination principle. | ‘The evaluation of Rydberg constant gives a correlation between four fundamental physical : constants namely m, e, ¢ and h. | 1.5 REFINEMENTS TO THE BOHR THEORY ‘The expression for the energy of an electton in the hydrogen atom is calculated assuming the nucleus to remain stationary, However, the nucleus actually oscillates slightly about (he cal Scanned with CamScanneree. College Chemistry 1 uM pane | energy is -2.17 x 107'8 J, Tonization energy AE = (E, ~ E,) 2? = O~(-2.17 x10 7 217 x 10-8 J, Jonization energy of hydrogen atom = 2.17 x 10-18 J. Jonization energy for one mole = 2.17 x 107% x 6.02 x 10% 3.06 x 1055 ; Fonization energy per mole of hydrogen = 13.00 x 105 Ju ample 10: Calculate the ionization energy per mole of Li?* ions. nergy of the first Bohr orbit = -2.17 x10“! Li* ion has only one electron (similar to H atom) and this electron is in the first orbit ie., Tonization energy AE = @,-,)2? = O- 2.17 x10-8 J) 3? 19.53 x 10-8 J 19.53 x 107" x 6.02 x 103 1.176 x 1073 = 1.176 x 10% KE Tonization energy per mole = 1.176 x 10'kJ. Ionization energy per mole Success of Bohr’s Theory Bohr's theory could explain the main features of atomic hydrogen spectrum and spectra of hydrogen-like species like He*, Li’* and Be™. It could easily explain the phenomenon ‘of absorption spectrum Bohr’s theory helps in the calculation of radii and energy of various orbits in hydrogen -atom and also the ionization potential 4. Iprovides a correlation between four fundamental physical constants namely mass of the electron, charge on the electron, velocity of light and Planck's constant. The fact that these values calculated on the basis of Bohr’s theory are in good agreement ‘with the experimental values proves the success of the theory. 1:52 Limitations of Bohr's Theory E. Ivfailsto explain the spectra and energy of atoms containing more than one electron. Infact, it fails to explain the spectrum of helium atom which has only 2 electrons. Z. It predicts the origin of only one spectral line from an electron between any {Wo ‘energy states but multiple or fine structure of spectral lines (a characteristic typical of atomic spectra) remains uriexplained. 3. This theory has no explanation for splitting of spectral lines in electric field (Stark effect) and in magnetic field (Zeeman effect). Scanned with CamScanner soilMechanics and Atomic Structure os Quantum gies of the stationary states in an atom containing more than 1 gnitude of ene! a 4, The mag! accurately calculated by the application of Bohr's theory. ‘one electron cannot be hea 5. does not throw light on the arrangement and distribution of electrons in atoms other than hydrogen. 6. A great drawback of 1.6 THE WAVE MECHANICAL CONCEPT OF ATOM Bohr’s theory which Was initially so successful! had (0 be abandoned only after 12 years, In spite of certain refinements, the Bohr theory could neither explain the details of multi- electron atoms nor provide a satisfactory picture of chemical bonding. In 1923, an important concept that electrons like light has dual particle-wave nature was introduced by Louis de Broglie. In 1926, a new approach called wave mechanics or quantum mechanics was developed independently by W. Heisenberg and E. Schrodinger to explain the the theory is its inability to explain molecule formation, strvcture of the atom. 4.7 DUAL NATURE OF MATTER — dE BROGLIE EQUATION In 1924, Louis de Broglie put forth the idea that if light waves can have particle like behaviour then particles of matter can perhaps show characteristics of wave under proper circumstances. The two fundamental equations obeyed by photons are : E = bvand E =v Combining the above two relations, E=m?=hy me? or v= h ie, h aet me where 1 is the wavelength m is the mass of the particle his Planek’s constant and cis velocity of light (3 x 108 msé') de Broglie postulated that a particle of mass m moving with a velocity v has an associated wave length 2. i de Broglie relation is =~ me Scanned with CamScannerCollege Chemistry - IT Tiomentum of the particle p, so that h he P The reason why wave properties are not commonly observed with particles is that in the case of ordinary particles, the wavelength is too small to be detected or measured, In the case of subatomic particles like electrons, the wavelength is of the order of nm. Their wave characteristics can be observed under proper circumstances The wave nature is predominant in micro jparticles whereas in macroparticles, the particle nature is more predominant, de Broglie concept does not mean that matter behaves like particles at some times and as waves at other times, The wave character is an inherent Property of all matter. Example 11: Calculate the wave length of the wave associated with a mass 1.0 kg moving with a speed 10 ms", h = 6.63 x 10 Js, = 6.63 x 10-5 m or 2 = 6.63 x 10° nm The wavelength is too small to be detected, Example 12: Calculate the wavelength of the wave associated with an electron moving with a velocity of 4.0 = 10° ms"!, Electronic mass = 9.1x 107?! kg, h = 6.63 x 10 Js, h Be oy 663 x 10-5 94110" kg xd x 10% ms = 18x 101m or A = 0.18 nm The wavelength is of the order nm and can be detected. (a) (by Fig. 1.3: (a) An allowed Bol orbit where the circumference of the orbit is an integral inutiple of sanelaths (6)A disallowed Bohs arbit since the circumference of the orbit is not an integral multiple of wavelengths eel . Scanned with CamScannerQuannum Mechanics and Atomic Structure According to de Broglie, for an electron to remain stationary it would have tobe a stand wave (no transport of energy) extending around the nucleus ina circular path the citcumferen of the orbit has to be an integral number of wavelengths as otherwise the wave would part cancel itself on each successive orbit and eventually the wave would not exist. In other word circumference 2nr = nh where r is the radius of the orbit and 2 is the wavelength of the electron wave. Substituting for A from de Broglie relation, Qn =n or mv The above relation is the same as Bohr's postulate ~ electrons move only in those orbit whose angular momentum is an integral multiple of h/2r. Thus the quantization of angut momentum assumed by Bohr comes directly from the wave nature of the electron. It is thus clear that all of the classical aspects of treating atomic structure would have to abandoned. The atom could not longer be compared (0 the solar system, for instead of “soli planets capable of precise measurement of position aiid momentum, one had a wave-like clect indefinite by its very nature. A new approach to the structure of the atom, considering the dus nature of the electron is needed. The theory of quantum mechanics was formulate simultaneously and independently by Werner Heisenberg and Erwin Schrodinger in 192 Important contributions to this theory were alse made by Paul Dirac, Max Born and wW. Paul ‘Schrodinger was awarded the Nobel Prize in physics in 1933 for his wave formulation of quant mechanics. : 1.8 HEISENBERG’S UNCERTAINTY PRINCIPLE ‘The principle of uncertainty, an important outcome of the dual nature. was formulated Wemer Heisenberg. According to the principle, it is impossible 10 know simultaneously bot the velocity (momentum) and the position of the particle accurately. Also, the more precise one of them is determined the more uncertain the other one becomes. The physical concept of this principle becomes clear if one realises that ail observations are to made by the impact of fight (photons). A large body suffers little alteration in its position or velocity by such an impact. On the other hand, a microscopic particle like an electron, suffers a change in its Incident Microscope velocity and path due to the impact of even a single Photon in photon of light uscd to observe it. Thus, it becomes impossible to measure precisely both the position -™ and momentum of microscopic bodies. In fact, the Final direction .. path and velocity of an electron as revealed by the and different impact of photons may be quite different from the velocity initial path and velocity, Fig. La: Change in the direction aed ‘momentum of an electron by he impact of a photon of light Scanned with CamScanner: College Chemistry. B ion of wavelength A is chosen to locate an electron, then accuracy of the position annot be greater than A. In order to locate the position of an electron accurately priate wavelength need to be chosen. The momentum of the incident photon : as its wavelength decreases (A= h/p). The momentui m of the electron being observeg i armtes due to collision between the electron and the incident photon. The extent of coat ‘e depends directly on the momentum of the photon. The higher the momentum of eae photon, the greater the disturbance and larger the uncertainty in measuring the ‘momentum of the electron, Thus, as the precision in locating the electron iscreases, the accuracy indetermining its momentum decreases. The product of the uncertainties will be comparable ‘in magnitade to Planck's constant. Ifa radiati ithe electron ¢: ndiation of approl h apx dx 2 ae where + Ap isthe uncertainty in measuring the momentum and Ax is the uncertainy in position. The above expression is the mathematical statement of Heisenberg’s uncertainy principle. Thus, itis seen that the uncertainties in measuring these two quantities vary inversely, so that Hone is determined fairly accurately, the other must be correspondingly less accurate. The imitation lies not upon the accuracy of the observing instruments or the methods of measurements tut is an inherent relationship in nature. Its thus not possible to pinpoint an electron in an atom in quantum mechanics, An electron may more correctly be associated with a definite energy ie. said to belong to a definite eneray level and not a particular orbit, In quantum mechanics, the term orbital is introduced in place of orbit. An orbital is deficed as a three dimensional region in space around the nucleus where there isa maximum probability of finding an electron having a certain energy. LO SCHRODINGER’S WAVE EQUATION Sinusoidal wave equation forms the basis of new quantum mechanics. The basis for handling all problems by quantum mechanics is the Schrodinger wave equation. This equation cannot be proved or derived but can be arrived at in a particular method (not discussed in this book). The ‘equation incorporates both particle behaviour in terms of mass m and wave behaviour in terms of wave function yfpsi). This equation is useful in solving all types of problems involving ‘atoms, electrons and molecules. The electron is associated with a dual nature — wave and particle (de Broglie's theory). The behaviour of an electron in an atom is best described by considering standing waves. [A standing wave is the resultant of two simple harmonic waves travelling with equal speed but ‘im opposite directions; the resultant wave does not move forward or backward}. A general equation for an electron moving in one dimension is given by 2nx Ly where y is a fuiiction of the displacement called wave function. The maximum amplitude of the wave 1s A and 2 is the wave length w= Asin Scanned with CamScannerQuantum Mec; 19 ‘anies and Atomic Structure Schrodin, er obta; 2 = bimy aaa T obtained ie’s relation thew an appropriate equation for the electron using de Broglic’s rel ‘alue of kinetic energy being 1/2 mv?, The equation is a > 2 2, SY Oy aty ant a at ET, n ye a2? MS equation can be written v]y =0 as v]y =0 where 2 j act 's called the Laplacian operator which operates only y. It is defined as v-(3 ay 3) This equation is also written in the form w (a - “SelB Ee Byer Or more simply, -tows vy = Ew 8n° or Hy = Ey where H is known as Hamiltonian operator, after Hamilton, a theoretical physicist. When H Operates on a wave function, a set of allowed or permissible energy values are obtained. 1.10 OPERATORS ~ HAMILTONIAN OPERATOR. Any mathematical operation such as addition, multiplication, square root, differentiation etc., can be represented by certain symbols known as operators. For example, in /3, J is a mathematical operator symbolising square root and 3 is the mathematical quantity on which it d operates, 3. J. + are all famitiar symbols for different mathematical operations. The 5 mathematical operator without the accompanying mathematical function has no meaning. Thus J has (0 be accompanied by a mathematical function or quantity. Generally, an operator is written with a symbol (*) overhead. Also, V2y does not mean y multiplied by V?. It means that the mathematical operator V2 operates upon the wave function y . In quantum mechanics, each physical property of classical mechanics, such as energy, tion, angular momentum, etc., of a system has a corresponding operator. posit Hamiltonian Operator ‘The total energy of a system is equal (0 the sum of kinetic and potential energies in lassical mechanics. This isgenerally writen as N. c H=E +E nek, Le. : Scanned with CamScanner. College Chemisy. | wh? ~ 8ma? +E corresponds to the energy of 1 value is quantized ay n can have valy integral values The energy levels are inversely proportional to ma?, o E= n=123, article is a one dimensional box and its ‘Thus if the particles are heavy or if the box is large, the energy levels are very close to one another. In such cases, quantization may not be obvious. (Classical behaviour). On the other hand, when m and a correspond to nomic dimensions, quantization can be detected experimentally and is in 1,12 POSTULATES OF QUANTUM MECHANICS nportant. A series of postulates based on the relationship between operators and quantum mechanics forms the basis for quantum mechanics. There is no direct proof for these postulates, The justification ies in the fact that there is agreement ofthe theoretical results with the experimental ones. A summary of the postulates are : (i) The physical state of a system at time tis fully described by the wave function y (x, x. 2,0. This wave function is a function of position coordinates and possibly time. (i) The possible wave function y (x,y, z,1) are obtained by solving appropriate Schrodinger equation. (Gai) The wave function y (x, y, 2, 0s its first deri finite and single valued for all values of x. ive, and second derivative are continuous, ‘The wave function y (x, y, 2, 0) is normalized which means Juv 21 vy’ is the complex conjugate of y. ‘The term i (equal to /—1) appearing in the function y is replaced by ~i in ye (iv) Every dynamical variable corresponding to a physically observable quantity can be sepresented by a linear operator. (7) Quantum mechanical operators corresponding to physical properties are obtained from the elassical expression in terms of the variable and converting thent to operators using Certain set of procedures. 1.13 SCHRODINGER WAVE EQUATION FOR HYDROGEN ATOM Schrodinger equation is applicable to all subatomic particles like electrons, atoms and molecules. The solution of this equation gives information about the ‘energies of the electron. The concept of atomic orbital which is of fundamental importance in understanding chemical bonding follows from this, Scanned with CamScanner‘Quantum Mechanics and Atomie Structure 23 The tiydto, ae gen atom and the hydrogen-like atoms (like helium He*, doubly charged lithium eeu ) is a two particle system consisting of an electron and atomic nucleus. The nucleus is “ med to be stationary as compared to the fast moving electron. The Schrodinger equation Seresponds to that of an electron of mass m, charge -e moving around the nucleus of charge + Zis tie atomic number. The reduced mass of the system 1 is used instead of m, where m+m, nm, m, is the mass of the nucleus The potential energy of the electron from a distance r from the nucleus is Schrodinger equation for hydrogen atom is then written as 8p Ze vty + SEE e vee Et er v=0 since there is a spherical symmetry in this system depending only of r, the Cartesian co- ordinates (x, y, 2) are converted into polar coordinates (r, @, 4), The two are related as x =rsin 8 cos ¢ y =rsin @ sing z=1cos @ The ranges of the coordinates are x from 010 =, 0 from Oto 7, and @ from 0 to 2x, Schrodinger equation is then written as 1a “) 2 2) 1 afr), 1 If ig), Pa (« ar) * Fino 30°"? aa) * YZ T= rsin0 sing Vig, 15: Relation between cartesian arnt polar coordinates Scanned with CamScanner* ae 2 College Chemistry - 11 Potential energy written as a product of ti Ons y = R@) 0@) 0) {isa function of r only, ie, where R() - @(@) - isa function of @ only and (6) - is. function of $ only. “This may be separated into three differential equations. Also, the partial derivatives can be replaced by ordinary derivatives as each function depends on only one variable. ao +m = 0 «++ (®) equation (©) equation 2 4 (sno) - m'® . 39 =0 13 (eB) f Fant a) r mand B are constants. The above equations can be selved to obtain the alfowed values of R, @ and @ and also the «+ (R) equation energy E. ‘On the basis of the solutions, tis found that the acceptable solutions are n=1,2,3... 1=0,1,2,...(n- 1) a m=-h-1+ 1,0, 1,2, ... for each value of The value of energy IE is given by 7 Ze! Bo seeathe wheres can have integral values starting from | i.e, n = I, 2, 3, ... and is called the principal Juana number. This value is identical with Bohr's expression for energy ‘The values of n, Jand m are the same as postulated earlier for the principal, azimuthal and magoetic quantum numbers of electrons. These values now have a theoretical basis as requiements.for the-solution of hydrogen and hydrogen-like atoms. he solutfons of Serodinger equation does not have the spin quantem number af an ‘This.yvas introduced (0 account for the electron spin, and the values are + 1/2 and 0 anticlockwise spin about its own axis, electroa. 1/2 for the clockwise and 41.14 EIGEN VALUES AND EIGEN FUNCTIONS ‘The Schrodinger-gquation can have several solutions, Out of these only some are acceptabie. yysical siteraion, the acceptable wave function must satisfy the following conditions. 1% . For any ph} Scanned with CamScannerQuantum Mechanics and Atomic Structure () y must have finite values. Gi) y must be single valued i.e., for each of the variables x, y, z. y can have only one value. (ii) y and its first derivative must be continuous with respect to its variables. ‘This means that sudden changes in w should net occur when its variables are changed. ‘When a wave function sati function. ‘The solutions that give acceptable values of the total energy are called eigen values. The corresponding wave functions which given eigen values for the energy are called eigen functions. In the case of atoms, eigen vaies correspond to a discrete set of energy values. 1.15 SIGNIFICANCE OF Y AND ¥? The wave function y is an amplitude function and has no physical meaning. w? gives the probability of finding the particle at a point at any given moment. Since the probability of finding a particle at a given point in space must be real (not imaginary), wy* is generaliy taken. y* is the complex conjugate of y. The product of yy* will always be a real, non negative quantity. Thus the product yy* gives the probability of locating an electron’ within a certain region of space. For a one dimensional problem. the domain is the length, for a two dimensional problem, it is an area and for 1 three dimensional problem, the domain is a volume. 1.16 WAVE FUNCTION FOR HYDROGEN ATOM The wave function for an electron in an atom is called an atomic orbital. The orbital for any electron is determined by the values of the quantum numbers n, and m s these three conditions, the function is called a well behaved Going back to the Schrodinger equation for hydrogen and hydrogen-like atoms, the wave function can be resolved into two factors. V(r, 8, 6) = R@® YO, 6) Rr) is the radial wave function Y(G, ) is the angular wave function and is the product of the two angular wave functions. 1.16.1 Radial Wave Function Radial wave function is independent of the angles 0 and >. The energy term E preset only in the R equation. Thus the allowed energies for a hydrogen-like atom depend only rr solutions of the R equation. i.¢., only on the principal quantum number, [The solution of equation gives the valucs of the principal quantum number), However, this is true ofl) hydrogenlike atoms. re . cil The radial wave function gives a distribution of electrons as a function, of distane from the nucleus. 1.16.2 Radial Distribution Function ” + in _ There are different ways of representing the probability distribution of electrons orbital. One method is to plot y? as a function of distance from the nucleus F. This N°. Scanned with CamScanner 2S Es: : College Chemistry - IT probability. density of finding the clectron at different points in space. A more informative method: of representation is in terms of the radial distribution functions. This gives the total probability of finding the electron in a spherical shell between r and r + dr, instead of just at a poiht. The spherical shell is actually the space between two concentric spheres one with radius r and the.other with a radius of r + dr. The volume of this spherical shell is 4nrdr. The probability of finding the electron in this small volume is obtained by mu!tiplying yy? by the volume ie, probability = 4rr2ydr This function 471?y? is called the radial distribution function. A plot of radial distribution function against r is shown in Fig 1.9 for electrons in 1s, 2s orbitals. For electrons in orbitals other than s i.e, / #0, (2p, 3d etc.,) angular dependence must also be taken into consideration for representing the probability. From the plot, it can be seen that for Is orbital there is a maximum at 0.0529am which is exactly the same as the Bohr radius. The orbital.is spherically symmetrical. — Is > Zc 3 g 4 8 a2 ° 1 0005 010015 0.20 025 Distance from nucleus (nm) a. : 2s a 3 £ & oa 05 06 07 of 0205 Distance from nucleus (nm) 2p Probab re Distance from nucleus (nm) Fig. L6: Plot of 4’? y’against distance Scanned with CamScannerQuantum Mechanics and Atomic Structure %. Hs pie Pas =2,1=0) orbital though spherically symmetrical, there are two' maxima in ihe let. his indicates that there is a probability of finding the electron in more than one oe yn je there is the maximum probability of finding the electron at the distance ¢ ponding to the highest peak, there is also a lesser probability of finding it at the distance ‘orresponding to the smaller peak. It is also seen that chance of finding the electron between the two distance or region is minimum. Such a region of zero electron density is called a node or a nodal sphere Similar plots for 4s, 4s can be drawn, There are two spherical nodes for 3s orbital and three for 4s orbital. 1.16.3 Angular Wave Function ‘As discussed earlier, the angular part of the wave function Y(@, 4) depends upon the angles @ and 9. It is a function of the quantum numbers /.and m. Generally, the @ and @ wave functions are considered together as both are concerned with the angular dependence of the orbitals. ‘The wave functions for p atomic orbitals depends on the angular co-ordinates @ and > in addition to r, From the probability plots it is seen that the probability of finding a p, electron is maximum along the z axis; itis zero in the x-y plane which is called the nodal plane. The electron density distribution is such that there are two lobes — one above and one below the x— y plans. In other words, it is ke two spheres touching at the origin, the centres lying on the 2 avis, (A nodal plane separates the two lobes). The atomic orbital has the shape of a dumb bell. . Similarly, p, orbital has two lobes along x axis with yz as the nodal plane; p, orbital has he nodal plane. The three p orbitals are similar in shape, two lobes along y-axis with x-z as U size and are mutually perpendicular. 2 z 2p, Fig. 1.7: Shapes of 2p orbitats 1.17 QUANTUM NUMBERS hanics, quantum: numbers are required to describe the distribution’ of electrons in an atom. From the solution of Schrodinger equation three quantum numbers namely, principal quantum number, azimuthal quantum number and magnetic quantum number are dbtained, These quantum numbers are useful to describe atomic orbitals and the electrons residing in them, The fourth quantum number Which refers to spin, a magnetic property of the Electron, arises from spectral evidence, In guantum mecl Scanned with CamScannerTa 2 College Chemistry - 11 28 principqnatam number, : This number is identical with Bohr’s integers and determines ge esate energy ofan electron. The value of n for circular orbits indicates roughly 10.4" sing face:as well as the distance between the nuclcus and the electron. This quantun the DIM mus presents the size of the election shell. It can have integral values 1, 2, 3 ete: sum nergy kvel is one nearest to the nucleus and has the least energy. For the yecend energy n= | “2. ese energy levels are also referred to as K, L, M.... shells, As the value of level: [es the déctron moves farther away from the nucicus. The size of energy level is larger incr geessesand ahe encrgy associated with it also increases, . as tevel- acimuthd quanti nunber |: This is also called the angular momentum quantum number, dian? orerbital quantum number. I< denotes the angular momentum of the electron in its subg arounkthe nucleus. It determines the shape of the orbital. This quantum number mot uishes abitals having the same principal quantum number (n) but having different shapes. dist tion diorbitals havirig the same value of n is frequently called a shell. Orbitals with ahame vatesof n and | are referred 10 as subshells. There is a limit to the number of the “polls thatmay be found in any shell or main energy level. The number of subshells that subse presestin a given energy level is given by the value of n itself for that level. Thus for may rey lewlin= I, there is only one subshell; the energy level n = 2, can have two subshells the 30 OF can haveintegral values from 0 to n- 1 ombitals with 1= 0, 1, 2, 3 are designated s, p, d, f orbitals respectively. These Iotters je oldspectral terms — sharp, principal, diffus> and fundamental, cesigh 1 0 1 2 Naneoftorbital | P d { agneticQaantun number, m : The electron behaves like a tiny magnet. This quantum describes the orientation of the orbitals.in. space, particularly in a strong magnetic snurmb jghin esubstell, the value of this quantum number depends on the value of /. For an ied pere 2:21 + | equivalent ways of orientation in space. In the absence of an electric or obit fel these orientations are degenerate, ie., they are identicat in energy. It can have mage ral vaes-including zero from ~! to +/. For / = 0, there is only one m value which is all inte gere are (21 + 1) ic., 3 m values which are —1, 0 and 1. co 121 of 1 nurrber:of m values indicate the number of orbitals in a subshell of value J. i allovedivalues of n, / and m:from the above rules and the possible orbitals are given ‘atian number's: This quantum number arises from the spectral evidence that the pins or rotates about its own axis. Uhlenbeck and Goudsmet introduced it in for the fine structure of spectral lines. This quantum number is important to of the electrons. Experiments show that spin angular momentum is also ‘two allowed orientations interpreted as clockwise and anticlockwise. Spinning 1 +5 and =~ , are +5: 8 o Scanned with CamScannerQuantum Mechanics and Atomic Structure : Table 1.2: Relation between Quantum Numbers 4* n ! m No.of orbitals Designation of orbitals 71 1 0 0 1 Is 4 2 0 0 1 2s 1 “104 3 3 0 0 1 | 1 -1,01 3 3Pys 3Py 3B, 2 -2,-1,0, 1,2 5 Bay 3p My 32 7-3 4.18 SHAPES OF ATOMIC ORBITALS bital has no well-defined shape because, the wave function characteristic of ori Sends from nucleus to infinity. However, a better understanding and clear picture chemical bonding between atoms is possible with specific shapes for orbitals. ‘Although an electron can be found anywhere, it is seen that most of the time is fo close to the nucleus. A plot of electron density verses distance from the nucleus indicates the electron density falls off rapidly with increase in distance from the nucleus. A bounda surface diagram that encloses about 90% of electron density is drawn te represent the orb Shapes of orbitals and even their relative sizes are thus based on the boundary surface diagr s orbitals s orbitals are spherical in shape. They differ in size depending on the value of the princi quantum number. That is, 2s orbital is larger in size than 1s orbital, 3s is larger than 2s and! on. They have fio directional characteristics. p orbitals There are three p orbitals in each subshell. The first set of p orbitals starts with the seed energy level (n = 2). The basic shape of p orbitals consists of two lobes arranged al straight line with the nucleus between the lobes i.e., dumb bell shaped. While the t orbitals are identical in size, shape and energy, they differ form one another in their oriental As they are set at right angles, the three p orbitals are shown as directed along the three % ys 2. They are designated as p,, Py» Py» the subscript indicating the axes along, whith orbitals are oriented, In.a n energy level, the three p orbitals are degenerate. d orbitals There are five d orbitals in each subshe ane designated as 30, 34 complicated than s and p HI starting with the third energy level (13) \ 3d,» 3d,2 _,2 and 3d,2, The shapes of these orbitals 4°") er orbitals and are as shown in Fig 1.1. Scanned with CamScanner30 f orbitals The shapes of f orbitals are difficult to represent. These start with the n= 4 energy level and are important to explain the properties of inner transition elements. ae 9 ope ++ Oo ¢ Sen 1.8: Shapes of atomie orbitals 1.19 ENERGIES OF ORBITALS The energy of the different orbitals in a given principal energy level or shell remains the same for hydrogen atom and for other one electron species like He*, Li**, In other words, the nergy of orbitals depend solely on the value of the principal quantum number. In the case of many electron atoms, the energy of an orbital depends on both the principal quantum number and the azimuthal quantum number. The orbital energy is found to depend on the presence of the other electrons in the lower Shetty levels so that the different orbitals belonging to same energy level have slightly different pa The huuclear effect on the outer electron is lowered by the electrons in the inner s. This is called the shielding or screening effect. Within a given energy level it is Scanned with CamScanner College Chemistry - 1 (mammaire tenn3d Quantum Mechanics and Atomic Structure found that the energy of the orbital levels, these differences are sufficient! s-inereases in the order s < p< 6s 6 6a un Is— aa Fig. 1.10: Orbital energy levels ina many Fig. LU: The order in which atomic subshells are electron atom. Note that the energy level filled in a many-electron atom. Start with the 1s orbital and move downward, following the direction The different types of or ordering of energies or orbitals that can be Figs. 1.13 and 1:14 depicts the energy | 4.20 ELECTRON DISTRIBUTION IN ATOMS ‘The aujbau process of filling up electrons in orbitals follow certain r governing the permissible values of the four quantum numbers. 1. Aufbau principle. The electrons go into the orbitals with the lowes 2, Pault’s Exclusion Principle : Wolfgang Pauli, an Austrian physi in 1925 which is stated as ~ 0 two electrons in an atom can depends on both n and I values. Is 9259 of arrows. Thus the order goes as fallo» 2p 93s 9 Jp 4s 93d > bitals are affected to different degrees. Thus there is no single universally accepted for all elements. jevel sequence in many electron systems. ules besides the ones energy. put forth this principle have all the four quantum numbers identical. Scanned with CamScannerz ate 2 . College Chemistry - I It simply means that if «wo electrons in an, atom have the same values for n, 1 and m, they must have different values of s, Thus, an electron entering the same orbital should have opposite spin. Also, no orbital can contain more than nwo electrons. It follows that nwo electrons in an atom can accupy the same orbital only if their spins are opposed. One of the applications of the above principle is that the maximum number of electrons that can be accommodsted in any subshell can he calculated. Name of orbital | Maximum number of electrons s 2 P 6 d 10 4 Ina principal energy level of quantum number n, the maximum number of electrons will be ‘2n?, Pauli wat awarded the Nobel Prize in physics for this work in 1945. 3. Hund’s rule of maximum multiplicity : This rule was put forth to indicate the most stable arrangemeni of electrons in an atom which is stated to be that of subshells with the greatest number of parallel spins. The rule is stated as - electron pairing in any orbital is not possible until all the orbitals of a given sei contain one vlectron each, all single elecirons being of parallel spin In simple terms, electrons occupy orbitals of equal energy singly before pairing can take place: witen electrons are placed singly they have parallel spins The rule is of importance in filling up p, d and f orbitals. For example, the electronic configuration of carbon is 1s, 2s, 2p,', 2p, and of nitrogen is I, 28%, 2p,',2p,!, 2p," 4, An electron enters the orbital where (it + 1) is minimum. In cases where (n + 1).values are equal for two orbitals, the one with lower n value is filled first. Examples: |. Consider (11+ 1) values for 3d and 4s orbitals. For 3d, (n+ 1) =3 +2 which is 5, and for 4s, (n + 1) = 4 +0 which is 4. ‘Thus electrons are filled up in 4s orbitals before 3p. % Consider (n + 1) vatlues for 2p and 3s orbitals. For 2p, in +) = 2+ | which is, 3, and for 3s, (n +) = 3+ 0 which is 3. The a value is lower in 2p; 2p orbitals are filled before 3s. 5. Blectrons prefer (0 enter those subshells which thereby get either completely filled or exactly half-filled. 4.28 ELECTRON CONFIGURATION OF ELEMENTS ‘A complete list of electron configurations for the ground state of the elements can be constructed on the basis of aufbau, principle and the other rules. Scanned with CamScannerQuantum Mechanics and Atomic Structure ‘A few exceptions are seen on comparison with the experimentally obtained configuya: “These exceptions occur where energy levels involved are exceedingly close together mde acy not accounted for in the above discussions play a role in such cases. Too much. importance is not to be placed on this type of deviation. Table 1.3: The Ground-state Electron Configurations of the Elements ‘Atomic | Symbol Electron Atomic Symbol Electronic number configuration | munber configuation — 1 H Ist 3 Ga (Ar4s?34 145! 2 He Is? 32 Ge [Arl4s?34!%p? 3 Li (He}2s! 33 As [Ari4s?34!4p3 4 Be [He]2s? 34 Se [Ar}4s?3d!%4pt 5 B [He}2s*2p! 35 Br [Arl4s?3d!4p5 6 c [He}2s?2p? * 36 Kr [Ar}4s?3d!%4p6 7 N [He]2s"2p? 37 Rb [Kr]5s' 8 ° [He}2s2p* 38 Sr iKrss? 9 F [He]2s*2p° 39 Y [Kr]ss"4d! 10 Ne {He]2s*2p® 40 Zr IKr]5s?4d* n Na [Ne]3s! A Nb [Kr]Ss!4d* 2 Mg [Ne]3s? 42 Mo [kr]5s'ad° 13 Al [Ne|3s*3p! 43 Te {Kr}5s*4d> 4 Si [Ne]3s°3p? 44 Ru [Kr}5s'4d” 15 P [Ne]3s?3p* 45 Rh {Kr]5s'4d° 16 s [Ne]3s?3p* 46 Pd (Krad? 7 cl {Ne]3s?3p* 47 Ag {Kr]5s'4a"" 18 Ar [Ne]3s?3p* 48 Cd [KrI5s*4d?? 19 K [Anas! 49 In Ukr}ssP4a"’sp! 20 Ca [Ar}4s? 50 Sn [kr}5s*4d"°5p? 2 Se [Ar]4s?3d! SI sb [krysstaa"’sp* 2 Ti fAr}4s?3d? 52 Te [Kr}5s%4d!%Sp" 2B v [Ar4s’3a3 53 I [Kr}5s*4d!*5p° 24 cr [Ar}4s!3a5 34 Xe [Kr}ss*4d!*5p* 25 Mn [Ar}4s*3a% 55 Cs [Xc}6s! 6 Fe. [Arl4s*3d® 56 Ba [xe]6s? 27 Co [Arl4s*3d? 57 La [xe]6s*5d" 28 Ni [Arl4stad® 58 Ce [xe}ostattsd! | 29 cu [ari4s!3a"® 59 Pr [xe]6s4F PS 0 Zn [Ar]ds?3d"? 60 Nd [xeI6s%4tt Scanned with CamScanner