Scribd Logo
Upload

Welcome to Scribd!

  • 350 views

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

    Uploaded by

    Alex-Mihai Ciubara
    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.

    Copyright:

    Attribution Non-Commercial (BY-NC)
    Download as PDF, TXT or read online from Scribd

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

    Uploaded by

    Alex-Mihai Ciubara
    350 views2 pages
    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.

    Original Description:

    Teorema lui Koopman

    Original Title

    Koopmans Theorem

    Copyright

    © Attribution Non-Commercial (BY-NC)

    Available Formats

    PDF, TXT or read online from Scribd

    Did you find this document useful?

    Is this content inappropriate?

    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.

    Copyright:

    Attribution Non-Commercial (BY-NC)
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    350 views2 pages

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

    Uploaded by

    Alex-Mihai Ciubara
    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.

    Copyright:

    Attribution Non-Commercial (BY-NC)
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    of 2

    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

    You might also like