Variation Method - Helium
Variation Method - Helium
Variation Method - Helium
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
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
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
1s(r1) and 1s(r2) are normalized eigenfunctions of one-electron Hamiltonians with charge Zeff :
* 1s(r1) 1s(r1) d1 = 1
* 1s(r2) 1s(r2) d2 = 1
2 =
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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:
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:
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
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