Variation Method- Helium If you guess a solution to the Schrdinger Equation, how do you find out how good

a guess you ^ have made? H i = Ei i cant be solved exactly: -2 h 1 Ze2 Ze2 e2 2 2 + + r + r i = Eii i ( ) 1 2 2m 4o 12 r1 2 but you have : E 1 guess E
1

2 better guess 3 better yet E Ei

E2 E3

Ei exact

The Variation Theorem guarantees that the trial energy is always greater than the exact energy.
^ H i = Ei i * ^ * i H i d = i Ei i d ^ * i H i d Ei = * i i d

solve for Ei:

^ *H d E = * d

is exact

E Ei

by the variation theorem 1 Zeff3 Z r /a Z r /a e eff 1 o e eff 2 o ao Zeff : variation parameter see Karplus and Porter 4.1.5

gs = 1s(r1) 1s(r2) =

* ^ gs H gs d e2 2 27 E = = Zeff 8 Zeff * 4 a o o gs gs d

minimize by changing Zeff: Zeff = 27/16 = 1.6875

dE e2 = 0 = (2 Zeff 27/8) dZeff 4o ao

2

2 Egs = 13.6 eV(Z2 eff /n1 + Zeff /n2) = -77.5 eV

(exp. -79.0 eV)

1s(r1) and 1s(r2) are normalized eigenfunctions of one-electron Hamiltonians with charge Zeff :

-2 h Zeff e2 1s(r1) = E1 1s(r1) 2 2m 1 4or1 normalization:

2 e 2 and eigenvalues: 1 = Zeff = -13.6 eV Z2 eff 4o ao

-2 h Zeff e2 1s(r2) = E2 1s(r2) 2 2m 2 4or2

* 1s(r1) 1s(r1) d1 = 1

* 1s(r2) 1s(r2) d2 = 1
2 =

2 e 2 Zeff = -13.6 eV Z2 eff 4o ao

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The exact Hamiltonian uses the full nuclear charge Z = 2. We can split the Coulomb portion of the exact Hamiltonian using Z = Zeff + (Z Zeff)
2 -2 -2 h h Ze2 (Z Zeff) e2 2 Zeff e 2 (r ) = (r ) 1s(r1) 1s 1 1s 1 4or1 2m 1 4or1 2m 1 4or1 2 -2 -2 h h Ze2 (Z Zeff) e2 2 2 Zeff e (r ) = (r ) 1s(r2) 1s 2 1s 2 4or2 2m 2 4or2 2m 2 4or2

Both electrons are in the same 1s-orbital so these two previous equations give the same energies. The electrons are identical, except for spin. To calculate the expectation value of the exact Hamiltonian,
* ^ ^ * 1s(r1) 1s(r2) H 1s(r1) 1s(r2) d, we find H 1s(r1) 1s(r2) using the last two equations:

-2 -2 h h Ze2 Ze2 e2 2 ^ H gs = 1s(r2) 2 (r ) + ( r ) (r ) + (r ) ( r ) 1s 1 1s 1 1s 2 4or12 1s 1 1s 2 2m 1 4or1 2m 2 4or2

2 (Z Zeff) e2 e2 e 2 = 1s(r1) 1s(r2) + ( r ) (r ) Zeff 1s(r1) 1s(r2) 2 4or1 4or12 1s 1 1s 2 4o ao

The variational energy for our guessed wave function is then:

2 (Z Zeff) e2 e2 e 2 * ^ E = * + Zeff 2 1s(r1) 1s(r2) H 1s(r1) 1s(r2) d = 4or1 4or12 4o ao

The first expectation value is the difference in the Coulomb attraction of an electron with a nucleus of charge Z and a nucleus of charge Zeff:

(Z Zeff) e2 e2 * = (Z Zeff) 1s (r1) * (r ) (r ) (r ) d1d2 1s 2 4or1 4o r1 1s 1 1s 2 e2 * (r ) (r ) d (r ) (r ) d1 = (Z Zeff) * 1s 2 1s 1 1s 2 2 4o r1 1s 1

normalization V

The first integral is the normalization for electron-2. The second integral is the expectation value of the potential energy for a one-electron atom with nuclear charge Zeff, V, see Problem 25.5.
2 (Z Zeff) e2 Zeff e 4 r = (Z Zeff) 4 a o o o 1

We evaluated the expectation value of the electron-electron repulsion for our perturbation treatment of the helium atom. We only need to substitute Zeff for Z:
eff * 4 r = 1s (r1) * 1s(r1) 1s(r2) d1d2 = 1s(r2) 8 4or12 4o ao o 12

e2

e2

5Z

e2

Setting Z = 2 gives the final result:

2 5Zeff e 2 E = ( Z2 eff 2 ZZeff + 2 Zeff + 8 ) 4 a o o

e2 2 27 27 E = Z = 27.211 eV Z2 Z Z 4o ao eff 8 eff eff 8 eff

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