Interpretation of Quantum Numbers : The three quantum numbers which arise in a natural way during search of acceptable solutions of the Schroedinger equation may be tabulated as follows : s(n = 1), itl We can interpret these quantum numbers in the following way : To interpret _m, we note that according to the Schroedinger theory of one-electron atom, the total energy of the bound states of the atom can have only following values “ Bah ln These eigenvalues which depend only on the quantum number 1, are the same as obtained by old quantum theory (Bohr model). They are in excellent agreement with experiment. Thus, m quantises the total energy of the atom. Hence n is called the ‘total’ or ‘principal’ quantum number. To interpret 1, we consider the radial wave equation (viit) : 1d {2a Brule Ms U)ee 34(?#)-[ ‘a {e vo} 5 IE 0 “The total energy E of the atom cohsists of the kinetic energy K and the potential energy clectrostatic) V of its electron. The kinetic energy K has two parts. Kyyjai due to electron’s motion toward or away from the nucleus and K,ysiu due to the motion around the nucleus. Thus E = Krutat + Korbitaa + V(r). Making this substitution in the radial eq, we obtain aif 2 | ddy par Br i ee Kida = eg: 54(72) + ae [Ratt Kea = | The radial equation is concerned only with the radial motion of the electron, hence it must be free from Kyiya- This is possible only when the last two terms cancel out each other that is, when$e Rost Ketel oF TT? be the angular momentum ofthe electron, then so that re Konia = 50 eo sey tue ee 7 or Beis ( Te or twat ted to the values Ht Oy By cs a= iif Since the quantum number 1 is restric ‘orbital’ quantum number, lar_momentum is identical isteplaced by VI + 1). ‘The expression for the angul Bohr-Sommerfeld theory, provided k ‘The various angular moment $: Pdf... corresponding to | = the corresponding total quantum m ith these letters. m = 2 and 1 = 0 isa 2s state, and one for which n = 3 a and so on, to that obtained in Thus, a state for which nd 1= 1 isa 3p state, The interpretation of m; comes We know that an electron revolving when the atom is placed in an external magnetic fi like a magnetic dipole in an exter eld ‘bout a nucleus is a minute curentloop and behaves smal magnetic field. Its rnagnetic potential energy depends Pon lis magnetic moment and its orientation with respect io the ere Bur the magnitude and direction of the magnetic moment depends upon the ‘magnitude and direction of the angular momentum L of the electron which, therefore, determines the magnetic potential energy. As we shall see, h Ls m 2a’ where my is restricted to the values 0,41, 42, £1, Thus, im, describes the ae pation of the orientation of C? in a magnetic field (known as space quantisation), and hence the quantisation of the magnetic energy of the eleciom ean, 1m, is called the ‘magnetic quantum number, ‘Thus, each of the eigenfunctions of one-electron atom is specified by three quantum ‘numbers, Land my; in which n determines the total nergy (eigenvalue), ! determines the angular momentum and m, determines the component ofthe angular momentum bf the electron, But fora given m. there are several different Possible values of 1, and for ach 1 there are several possible values of my. Hence sexes different. cigentunctionscorrespond to exactly the same eigenvalue E,. Such eigenfunctions are said to be “degenerate”. 6. Electron Probability Density The quantum-mechanical description of the energy states of one-electron atom is similar in many respects to that from the old quantum theory. Yet there are striking differences regarding the motion of the electron within the atom. Quantum mechanically, the electron cannot be considered as moving around the nucleus in definite orbits. We can consider only the relative probability of finding the electron in volume elements at various locations. ‘The electron wave function in a one-electron atom is given by Wrctim, (8,6) = Ry. 1(#) Om, (0) Pn, ) + where R,O,@ describe how y varies with 1,0 and respectively. The three-dimensional electron probability density y [? may therefore be written as lwP =IRPIOFIe?, where ly = wy", etc. ‘The azimuthal probability density |I, however, does not play any part in determining the probability density Iw? , because lo? = oo amy (acim) 2 which is a constant. This means that the probability density I y I? does not depend on 6. It is symmetrical about the z-axis, regardless of the quantum state of the electron. Thus, ly!’ is completely specified by |R F107 Let us first consider the e 2 i) dependence of Iw on IRI, We Ehoe tie radial probability density | P(A), such that P(r)dr isthe probability of finding the electron at a distance between r and r+ dr a from the nucleus. It is given by P(r dr = IRE (Ar dr), 4 where 4a/dr is the volume P(A) enclosed between spheres of radii r and r+ dr. The graphs of P(r) against r for certain values of 1 and f (states Is, 2s, 2p) for the hydrogen atom (Z = 1) are shown in Fig. 2, We see that for the states P(2) Is and 2p the maxima of the curves | fall exactly at ag and 4a), which are the radii of Bohr orbits 1g (m=1, b=0)wren: Lay corresponding to n = 1 and n = 2 respectively. For the state 2s, however, the m ‘maximum is a little deviated from 4 ay , and a weaker ‘maximum also exist. Thus, where the electron is most likely to be found at the locations of Bohr orbits, it has a finj Probability of being found elsewhere also ‘The average distance ofthe electron from the nucleus is given by Ir Pinar (On evaluating the integral, we get Aled - 4D } Zz 3 Cf where ay is the smallest Bohr orbit, Orbit if & is replaced by (1 + 1). The value of 7 is evaluated This is same as for the Boht-Sommerfeld ellipti ofthe probability density curv about its maximum (Fig. 2) 1 the probability of finding the electron near the |. This isin agreement with Sommerfeld ellie when passing near the nucleus than when fapQuantum mecnanses vy rysreper’ 0). This in fact) for an s-state ( ‘The angular probability density 1 Fis constant ty Ly? has the means that, since ||? is also a constant, the electron probability densi the probability fame value at a given r in all directions. In other words. for s-states, density \y is spherically symmetrical about the nucleus (independent of @ and @ ) For other states, however, | varies with @ and takes on largest values in definite directions. In a given state (other than s-state), the concentration of probability density shifts from the z-axis to the plane perpendicular to the z-axis as the absolute value of m increases from 0 to | ‘The three-dimensional character of |” been shown in Fig. 4. Each figure, which is infact an clectror 4 24 2p 2p nel, L=0,mz0 2=2, for a few states of one-electron atom has n-cloud, is symmetrical about the caxis which is vertical to the plane of paper. All sstates (I= 0) ave spherically-symmetric, with the maximum value of probability density function | y Pat the origin and decreasing uniformly in all radial directions. The p-states (J = 1), and also other higher states, show @-dependence. ‘The functions | yi displayed in these figures, in general, have spherical and conical nodal surfaces, defined by certain values of r and @, where they vanish, that i, the tHectron is never found there. For example, inthe 2s-state there is a spherical nodal shell between an inner sphere and an outer spherical shell, The nodal surfaces are a consequence ofthe fact that the wave functions for a bound particle must be standing waves with fixed nodes. Conclusion : There are many points at which the quantum mechanical theory of the one-electron atom corresponds quite closely to the old quantum: Bohr-Sommerfeld theory. For example, both theories result in the quantisation of the total energy of the atom, giving same energy values. Similarly, both agree on the quantisation of the angular momentum, But whereas in the old theory the quantum numbers are introduced as postulates, in quantum mechanics they appear automatically while finding the acceptable solutions of the wave equation. ‘As far as the actual motion of the electron within the atom is concerned, the two theories differ appreciably. In the old quantum theory, the electron traces fixed elliptic orbits whose size, shape and orientation are determined by quantisation rules. In quantum. mechanics, on the other hand, the electron cannot be alloted definite orbits; it has only relative probabilities of being found at various locations. The probability is of course ‘maximum at the locations of the Bohr-Sommerfeld orbits, but not zero elsewhere. Hence in quantum mechanics the electron is smeared out over the whole of space like an electronof the electron. As we shall see, the f the wave nature f 2 aining the spectra of cloud. This is clearly a consequence : quantum mechanical theory has been very successful in expl aaa tron atoms and te relative intensity of spectral lines. ‘A paradox regarding s-orbits : According 10 ‘Bohr-Sommerfeld theory, the angular momentum for an electron in the s-orbit is Lak (k=1) whereas according to quantum mechanics iti$ L=Wd+D 357% =o) From measurements of atomic specra, the quantum mechanical prediction of zero orbital angular momentum for the s-state comes out to be the comest ote. The zero angular Jectron’s motion is entirely radial. Therefore, in terms of Bohr ‘momentum means that the el : theory, the s-orbit would be a radial oscillation (pendulum orbit) in which the electron would pass directly through the nucleus (which is actually impossible), and the oscillation could take place along any direction in space. This would correspond to a spherically symmetrical probability density (or charge distribution) about the nucleus. This is in agreement with quantum mechanics which predicts that all s-states are spherically symmetrical. Thus, the difficulty of the s-orbit passing thrugh the nucleus was removed quantum mechanically. Degeneracy of Atomic Levels: It is also noticed ‘ ci pncesl qooaun omuber Be eof tates ea in the Bohr theory, but as / and m have a number of values for have a number of possible wave functions for a given ee we refer as the degeneracy of a level, There are of str suneasperee-titenaptoomamcnite i sre ‘ctpmietwen Gees ite enenl a-i £ (i+ ty=2"E [+21 F. 0 =n ing is that a given energy level is split up into n” energy levels, ioe indistinguishable from the point of view of energy. The degeneracy of various levels is shown in figure 3. It is to be noted that (2/+1) wave func- tions with the same n and / are said to form a complete subgroup and n® wave functions with the same n, a complete group. Fur- thermore, the degeneracy of a level is represented by a separate eigen function and the eigen functions distinguish among themselves by different values of ! and m. The degeneracy which pouieaies mae Fig 3. Degeneracy of Hydrogen Levels Pears when allowance is made for relativistic variation of mass. A small deviation then appears in the energy for a level with different J but equal Fini difference like Bohr theory explains the fine structure of specteal is noticed when the allowance is made for electron spin, {B) Dependence of wave function on the angles @ and ¢: The ‘one-electron wave functions, determined for hydrogen-like atoms, are also Known as atomic orbitals.* The important feature about these exbiae Baa aistion with diferent values of @ and 9. Really speaking. the angles 6 and ¢ determine the geometry of the atom. Iti also cheerven that sea? Scpendence of radial wave function is the same for various values of lim @ given shell, The meaning is that in a given shell, the subshells are on the basis of their angular dependence, "A sate Of an electron described by the set of quantum nuynbers is called an orbital, Soria pe cons na ttt oa Go emcee ction ata Hil epee «hed tla. The yp Ye teeny46-2 Some General Properties of One Electron Wave Functions table 5 contains the normalized eigenfunctions for different states, calculated from the relation Vnin = AninBnd) Oin(8) Onl), where Anim Stands for normalization constant. In Table 5 the real form of & function is used which is useful in chemical ponding. It is to be noted that the functions Wap, Wap, ANd Wry, are identical except for orientation in space, Similarly, the functions Wag...» Wn. Wad,,, ANd Way ate identical except for orientation, while Oz, is different. Fig. 11 represents these functions on an exaggerated scale. Table 5: Normalized Hydrogen Like Wave Functions ‘Each of the states is axially symmetric about a polar axis (Z-axis) in the plane of the figure, Now since in quantum mechanics the concept of definite orbits is discarded, we speak that the electron is smeared out over whole of the surface and hence forms the electron cloud round the nucleus. The electron cloud as is represented in the picture does not mean that the electron occupies at one time the whole of the space occupied by the cloud, but the density of the electron cloud at a point gives only the probability of finding the electron at the point (the electron here is considred as a point charge), It should be noted that the electron is most often found in the outermost spherical shell, in spite of greater density in the middle of the cloud, since this has much greater extent, for example, in the concentric subshells for different 1 values. The density of electron clouds is measuredsadaeet rea seam eo neem eer te2 Fig. 11. The three-dimensional character of the probability distribution y*y for 4ifferent values of n, (and m. from the brightness of the photographs. These photographs are obtained by observing a number of H atoms in the same state. ‘The states with /=0 and n=1,2,3 are spherically symmetrical. As discussed before, for the states defined by the n values greater than one, alternate bright and dark rings appear and these rings correspond (0 the nodal surfaces of the different states where the electron can never be found. For the values of />0, the figure shows complicated nature and we get somewhat conical and spherical nodal surfaces. For n = 2, 1= 1, m=, we get two lobes extending in either direction along the polar axis, and for n=4,1=3,m=1, we get three nodal surfaces, two conical surfaces and a plane passing through the Z-axis. It is worthy to note here that in the problems of practical importance such as chemical binding, use is made of eigen states which have lobes extending in directions other than along the Z-axis. These states, mathematically, are expressed as linear combination of two eigen functions; for example,Wave functions for H atom * Energy depends only on n for H atom, not on | or m * Shape of wave function depends on n, |, and m + A function of one particle is called an “orbital” + 1=0 is an s orbital is a p orbital (m= is ad orbital (m= a2, d.*) + |=3 is an f orbital (7 of these)... etc... . Al these functions are 3D functions; hard to plot... +0, 1 => Py, Py, Pe) 1,0, 1,2 => dy, dy dye,H atom S orbitalsH atom p orbitalsH atom d orbitals Ree aay