CHAPTER V ‘THE HYDROGEN ATOM ‘Phe problem of the structure of the hydrogen atom is the most important problem in the field of atomic and molecular structure, not only because the theoretical treatment of this atom is simpler than that of other atoms and of molecules, but also because it forms the basis for the discussion of more complex atomic sys- tems. ‘The wave-mechanieal treatment of polyclectronic atoms and of molecules is usually closely related in procedure to that of the hydrogen atom, often being based on the use of hydrogen; nt tive like or closely related wave functions. Moreover, almos exception the applications of qualitative and semiq \ave-mechanical arguments to chemistry involve th ‘which occur in the treatment of the hydrogen atom. "The hydrogen atom has held a prominent place in the develop- ment of physical theory. The first spectral series expressed by & ‘simple formula was the Balmer series of hydrogen. Bohr's treatment of the hydrogen atom marked the beginning of the old jructure, and wave mechanics had~ le only jcated systems not yet having been separated and solved gy levels are discussed. Vie] THE SOLUTION OF THE WAVE EQUATION 113 tions 19 and 20 include the definition of certain functic Tagen and Laguerefunetions, which occur inthe hydogen stom wave fants nd the dicion of ht prope, A eee ne ‘of the wave functions themselves is given NOMIAL METHOD AND THE DI or oh tna ug 18a. The Separation of the Wave Equation. ‘Transla- Pelosi al mpe ag =. two interacting point particles, the interaction being that due to the Coulomb attraction of their electrical char for generality ascribe to the nucleus the charge +: Semin siege oe e Cartesian coordinates of the nucleus and bd ou and for Chel? asia wave equation has the form z (a Or, ae 1 (a%s Ae Oe) | 1 (ate Oe | Oe mae + t+ 5H) + (Oe + ie + Se) Set + Fe Ws — Vr = 0, (08-1) in which the hydrogena us r energy due to the field then being in whieh Bis the strength of the field, considered as bx direction of the 2 axis. To effect the separation, we introduce the new variables zr, y, and z, which ate the Cartesian coordinates of the center of mass of tho system,and 7,9, and y, the polar coordinates of the second particle relative to the first. ‘These coordinates are related to the Cartesian coordinates of the two particles by the equations only on r, 8, and g. Bac stant. The resulting equations (08-29 OF | OF OF, Bem + m as-2) de + Be tet tm , and as-2e \ Large, 1 ay 12/06 (18-2d) . Rae 0) + int dg? + TaN rain dain @ = ys — 9 (18-29 aint a6? + Fsind ool Rae us) ‘he int ct those new independent: vat ‘quation 18-1 is easily made in the usual way. The resultant (SE +agt + 1 1a 2 wae + mins”) + SE UWs — V(r, 8, evr = 0. required. energy of the system as the energy of the system, Equation 18-7 is ide: 18-3) ‘In this equation the symbol « has been introduced to represent ‘the quantity : as) any, ms)" Section Eqs. 2-2: zis the reducefl mass of the system, already discussed in Section 24 (Bas. 2-25). ‘2d in the classical treatment of this problem. Tt willbe noticed thatthe quantity in the frst set of parentheses is the Laplacian of yr in the Cartesian coordinates 2 ys and 2, shad the quantity in the rt st of braces isthe Leplacian in the polar coordinates r, 3, and ¢ (Appendix IV). function V is a funetion of r alone, V=ve, fe this equation by ex a function of x, his in Bauation 18-8 and dividing und that the equation is the sum oft ene of which is dependent only on 2, y, and 2 part must heneo be equal to a cou In our further discussion we rom the translati l with the wave equat le of mass 4 under the influence of a pot #). This identity corresponds to the classi ourselves to the ease in whi Equation 18-7 can be further separnted. We write 9) = Bir) -0(9) - (0)116 ‘THE HYDROGEN ATOM vite ‘on introducing this in Equation 18-7 and dividing by RO#, it becomes: 1a 1a ae) eat + int oe det * Fain v0 a" "as, 488407 — veo} =o. ato) ‘On multiplying through by r sin? 9, the remaining part of the second term, 22%, which could only be a function of the inde- » & dg “ pendent variable g, is seen to be equal to terms independent of ¢. Hence this term must be equal to a constant, which we eall —m?: PF _ me, (18-11) ‘The equation in @ and r then ean be written as nal) aot mle) OF =o. ‘The part ofthis equation containing the seeond and third terms is sade of r and the remaining part is independent of 3, so that we can equate each to a constant. If we set the 9 terms equal to the constant —8, and the r terms equal to +8, we Stain the following equations, after multiplication by 0 and by B/r, respectively: hg Bono) — gto +90 -0 cs and 14 Sn 4 SH W — voyIR =o. (18-19) Pra a8) _ Bn at — VO) a Equations 18-11, 18-12, and 18-19 are now to be solved in dider to detormine the allowed. values of the energy ‘The sequence of station i te flowing We eo Gd tht uation 18-11 possesses acceptable solutions only for certain ert ehepartmclerm. Introduig thes in Baton 18-1, We find that ie then, possoses acceptable nlutions only for Certain values of 6. Finaly, we introduce these values of 8 Veith] THE SOLUTION OP THE WAVE EQUATION — 117 in Equation 18-13 and find that this equation then possesses acceptable solutions only for certain values of W. These are the values of the energy for the stationary states of the system. It may be mentioned that the wave equation for the hydrogen ‘atom can also be separated in coordinate systems other than the polar coordinates r, 3, and g which we have chosen, and for some Purposes another coordinate system may be especially appro- priate, as, for example, in the treatment of the Stark effect, for which (as shown by Schrédinger in his third paper) it is convenient to use parabolic coordinates. 18b. The Solution of the » Equation.—As Section 17, the ms of Equation 18-11, coordinate y, are = Le, Ole) = Faget (asa) In order for the function to be single-valued at the point ¢ = 0 (which is identical with ¢ = 2x), the parameter m must be equal to an integer. The independent acceptable solutions of the ¢ equation are hence given by Equation 18-14, with m= 0, Fi, 42,05, -1, -2,+ +5 these values are usually: +++ , it being understood that positive and negative values correspond to distinct solutions, ‘The constant m is ealled the magnetic quantum number, Tt is the analogue of the same quantum number in the old-quantum- theory treatment, (See. 76). The factor 1/1/2r is introduced in order to normalize the functions #4(¢), which then satisfy the equation Se elede = 1. (8-15) It may be pointed out that for a given value of |m| (the absolute value of m), the two functions #q(¢) and ®s.i(¢) satisfy the same differet the equation. ‘The sum and the difference of these two fun are the cosine and sine functions. It is sometimes conveni to use these in place of the complex exponential functions as the independent solutions of the wave equation, the normalized solutions then being