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Koopman's Theorem and The Roothan Equations: F T J K J K

Koopman's theorem relates the orbital energies calculated from the Hartree-Fock equations to ionization potentials. It states that the orbital energy of the highest occupied orbital approximates the energy required to remove an electron from that orbital (the ionization potential). The Hartree-Fock equations are derived and involve terms for the kinetic energy, nuclear attraction, Coulomb repulsion, and exchange interaction between electrons. The Roothaan equations allow solving the Hartree-Fock equations numerically by expanding the molecular orbitals in a basis set and diagonalizing the Fock operator.

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Alex-Mihai Ciubara
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724 views2 pages

Koopman's Theorem and The Roothan Equations: F T J K J K

Koopman's theorem relates the orbital energies calculated from the Hartree-Fock equations to ionization potentials. It states that the orbital energy of the highest occupied orbital approximates the energy required to remove an electron from that orbital (the ionization potential). The Hartree-Fock equations are derived and involve terms for the kinetic energy, nuclear attraction, Coulomb repulsion, and exchange interaction between electrons. The Roothaan equations allow solving the Hartree-Fock equations numerically by expanding the molecular orbitals in a basis set and diagonalizing the Fock operator.

Uploaded by

Alex-Mihai Ciubara
Copyright
© Attribution Non-Commercial (BY-NC)
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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Koopmans Theorem and the Roothan Equations

The HF equatios are Fi i = i i , i = 1K n Fi = Ti + Ji Ki Ji = Coulomb operator in the average field of ji electrons Ki = Exchange operator in the average field of ji electrons i are the orbital energies. They are a good approximation to the magnitude of the ionization energy for an electron in the orbital i.

Proof Clearly i F i = i , where i = i h i +

i Tij Kij i

occupied

For electron ionization (detachment) I.P. = EN-EN-1 take electron from kth orbital = 1 2 L k k +1 L HN 1 2 L k k +1 L 1 2 L k +1 L HN 1 12 L k +1 L = k h k + J kj Kkj = k q.e.d.
j

Koopmans Theorem 1 of 1

HF Roothan equations Return to the Hartree-Fock z electron 1s2s


(1, 2 ) = 1 (1) (2 ) (1) (2) (1s(1)2 s + 1s(2)2 s(1)) 2 2

2 2 2 T Ze + 2s(2 ) e 2 s(2) 2 s(2) e 1s( 2) (r ) = 0 1 1s 1 1 r1 r r 12 12 2 2 2 T Ze + 2s(1) e 2 s(1) 2 s(1) e 1s(1) (r ) = 0 1 2s 2 1 r r12 r 2 12

(1)

(2)

Write

s 1 s = C1 L XL L 2s 2 s = CL XL L

where {XL } is a complete set of functions. In atomic case these functions are orthonormal. Substitute into eqs. (1) and (2) respectively, and proceed as usual to get the linear equations which lead to diagonalization of a Hamiltonian matrix. Start with a zero order guess for
1s

and

2 s

as usual, by choosing one coefficient C to be one and the

others zero to evaluate the coulomb and exchange operators. Then diagonalize and get a new set of Cs. Use these to evaluate the coulomb and exchange operators, and diagonalize again. Continue until the process converges and the orbital energies converge.

Koopmans Theorem 2 of 2

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