5.14.4 Approximation Method for the Ground State of the Helium. at In order to solve these approximate methods for multi electron atoms like helium atom, L etc, we shall try to calculate the energy of the ground state of the helium atom by using both methods... by the application ofthe fst order TH) ty WaPo HS. inst Mal we will ty Msolye approximation for ene ground state of helium atom. The Hamiltonian operator, H for the helium atom (or two-electron atoms such as Li*, Be*’ etc.) is (if we do not consider the terms arising from the motion of the nucleus). Ze ed (5.238) hs where V, and V, are the well-known Laplacian operators for electrons 1 and 2. The distances of these electrons from the nucleus is given by r; and rs. The distance between the two electrons is oe by ri) and Z is the effective nuclear charge. It is here recommended to use atomic units for purpose of simplifying the calculation of integrals involved in problems of this type, i.e. two- i nme Rr electron atoms, This fs done by expressing distances in terms of the Bohr radius, & ‘The distances terms of Bohr radius modifies as, = a)Rysry = ayRos Fig ‘The Hamiltonian operator thus becomes, 1 tne (5.239) 2 or in units of Zz +V5 PVE) Fate (5240) (On applying the methods af the perturbation theory to helium atom, we obtain = H+ HO Bet where. RR: (5.241) (5.242)‘The eigenfunction for the ground state, ic. unperturbed system or zeroth eigentunetions ean be separated as: Ay! = (5.243) genfunction and eigenvalue for unperturbed system are set equal {0 y° = y/),¥/ EY, +E%,, then Eq, (5.243) is immediately separable into two equations, Lyayo af ne 42 lye vives +(e, +2 }y 0 (5.244a) baie, aft a 2 let svi’, «(28 +2) ‘The above two equations, ie., Eqs. (5.244a) and (5.244) are similar fo equation fora hydrogen like atom with nuclear charge Z. For the ground state of the helitim atom, we therefore have = (5.244b) (5.245) Here £,s(H) isdefined as the energy of the ground state of the hydrogen atom and in ordinary. 1 2a ppetturhation theorem is given by B= [Jy Ho y'drar, units its value is — ‘The first order correction to the energy according t Eq. (5.240) in OD ce thg tthe = £2 [anaes (5.246) where dt, = Rsin8,dR,d0,dd, and dt, = Risin@,dR,d0,d6, ‘The value of energy in Eq. (5.246) cannot be evaluated because of the presence of the term VR,» in the integral. In a very similar manner as in harmonic escillator, the quantity 1/R can be expanded in terms of the associated Legendre’s polynomial as d= |mpt RE a Epi ae P{"'(cos6,)PJ"(cos8, )e™O"%! (3.247)Here R- signifies that it is smaller and R. signifies that it is larger of the qualities R, and Rs, respectively, Here the wave functions do not involve the angles unambiguously. Only the constant functions, i.e. Pj'(cos6,) and Fj'(cos@,) are involved in the wave functions. As we know, the associated Legendre’s polynomial are orthogonal to each other, all the terms in the summation will vanish except for those J = 0, m = 0. For these terms P)(cos@,)= 1 so that Eq. (5.246) becomes DE ce th gt ee gl (5.248) {8898 solution SE integration over i angles in above:equation gives a factor én,s0 we have left only the integral over R; and R which may be solved in a simple manner to give Bde PE (5.249) ‘The energy for the lowest ground state of helium atom is therefore given as E=E°+E" (22 i) 2a, 5 -(22-3 Jasen (5.250) ee ee eee that is ilminmam energy required remove an electron from ft IN BE sven as 2_5 s 4 (2 ~32}4;cc=Rejcctn =3n60)= 2040¥ But the actual value is 24.58 eV (observed value) so that our calculated value is in error by 4.18 6V ot about 16 percent. fiigresules SF tet order are scons Wbe plaisible if we compare the total binding energy. The values of calculated and observed total binding energy are: calculated !! (13,6) = 74,8eV, observed 78.98 eV. An error of 4.18 eV, i.e. about 5 percent. Although the magnitude of actual error is the same in both cases but the percentage error ‘course decreased in case of total binding energy. 5.15 VARIATION METHOD APPLIED TO HELIUM ATOM Laos ap variation method to solve SWE for helium atom. In order to solve variation method for’ ‘we may choose a reasonable trial eigenfunction for use in the variation method. Lets consider hat onc OF Ha loctrns Ot ti lim SB sn an excited state SW other in‘the ground state, The first electton is subjected to the full attractive force of the nucleus because itis in ground state and considered to be very close to nucleus, so that Y, should be essentially the same as in Eq. (5.245). As the (Is) electron sereerss the nucleus more or less completely and hence the electron in the excited state, moves essentially inthe fleld of nucleus of charge ¢ and so rh foe ob ected sats shold appronirnate store closely a a yidvogen weve function With Z= 1L Above said generalization suggests that a good rial eigenfunction would be such that ze = where Z’ is effective nuclear charge between the electron 1 and 2, the best value of Eq. (5.251) can be determined by solving y for energy. The eigenfunction written above in Ba. (5.251) is the solution of the equation: v 6251) aly 6252) In units of <— zt & BE) =22"E,(H) We can solve for the integral given as B= | fw awarae, (8.253) ‘Vere 77s detined as es We ean define Hy as zz 1 hy = 22 yg 254) e [ Be zy : Le (5.254) Ey -(z-z/ +44 \yas sy v mim) ta ‘The integral in Eq, (5.253) is limited to E= Ey -(Z= aol [Pena + Janes] [Bena (5.255) ‘The values ofthe tw only in the exchange of integrals in the brackets of the above equation are equal, as they differ subscripts 1 and 2. The value of the fist of the integral is, 16x? 2 fermen fe 0 R, (5.256)The last integral is identical with Eq. (5.246) ifZ is replaced by 2’. The result for the energy is thus given as E=Ej-22(2-Z')2—+22" a 8 a = [22 4422-7) ~i2'|p.u 5 = [22 +422" 2’ et (5.257) 4 As per variation theorem, one can obtain the best approximation to the true energy by giving Z’ ‘the value which will make the energy a minimum. Hence, (az+42-S)ran=0 (5.258) (5.259) ‘The first ionization potential of helium atom is thus given as [+ 2) 4 16 Here the difference between calculated and observed value of first ionization potential in case M8 HVE HEGRE thus reduced 8. 1.53:eV or about’6 percent. THM total binding ebergy is calculated to be 77.45 eV as compared to the experimental value 78.98 eV or an error of about 2 percent which is much less as compared to ‘method applied to helium atom. Dy sultbly modifying HUGUHMGA WING, ie. riroaucing rior parameters int HW tal tigentinction y we can approach more HH more closely i iBlexperimemial result tn fect very good results are obtained, ifthe variable R,. is unequivocally introduced into the trial eigenfunction. For example, Hylleras has used the trial eigenfunction as E,s(H) .695(13.6) = 23.05eV yaalerrrraecr,)} (5.260) where, isl wonmalization fect Ml 2’ BBC ate adjustable vost: Value for 8 firs ionization potential of the helium atom thus cbtained by variation method isin etror by only 0.34 eV. in order Ed radace Hieron, more general fonctions were uiod that i,