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    General Chemistry (CHEM F111) Lecture-11 13/04/2023

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    The document discusses many electron atoms within the orbital approximation. It explains that the Schrodinger equation cannot be solved exactly for multi-electron atoms, but the orbital approximation allows treating each electron independently within effective hydrogen-like orbitals. It describes how the Pauli exclusion principle requires the wavefunction to be antisymmetric under particle exchange. For systems with unpaired electrons, the spatial and spin parts of the wavefunction combine to make the total wavefunction antisymmetric.

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    General Chemistry (CHEM F111) Lecture-11 13/04/2023

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    The document discusses many electron atoms within the orbital approximation. It explains that the Schrodinger equation cannot be solved exactly for multi-electron atoms, but the orbital approximation allows treating each electron independently within effective hydrogen-like orbitals. It describes how the Pauli exclusion principle requires the wavefunction to be antisymmetric under particle exchange. For systems with unpaired electrons, the spatial and spin parts of the wavefunction combine to make the total wavefunction antisymmetric.

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    The document discusses many electron atoms within the orbital approximation. It explains that the Schrodinger equation cannot be solved exactly for multi-electron atoms, but the orbital approximation allows treating each electron independently within effective hydrogen-like orbitals. It describes how the Pauli exclusion principle requires the wavefunction to be antisymmetric under particle exchange. For systems with unpaired electrons, the spatial and spin parts of the wavefunction combine to make the total wavefunction antisymmetric.

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    Download as ppt, pdf, or txt
    17 views15 pages

    General Chemistry (CHEM F111) Lecture-11 13/04/2023

    Uploaded by

    Please Help BPHC
    The document discusses many electron atoms within the orbital approximation. It explains that the Schrodinger equation cannot be solved exactly for multi-electron atoms, but the orbital approximation allows treating each electron independently within effective hydrogen-like orbitals. It describes how the Pauli exclusion principle requires the wavefunction to be antisymmetric under particle exchange. For systems with unpaired electrons, the spatial and spin parts of the wavefunction combine to make the total wavefunction antisymmetric.

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    General Chemistry (CHEM

    F111)

    Lecture-11
    13/04/2023
    Recap

    • Stern Gerlach Experiment – Spin

    • Spin Orbitals

    • Spectral Transitions and Selection Rules

    • Many electron atoms (orbital approximation)


    Today’s topic
    • Many electron atoms (orbital approximation)

    • Antisymmetry (Pauli) principle

    • Antisymmetry in the systems with ‘unpaired’


    electrons

    • Periodicity
    Many electron atoms
    The Schrodinger equation cannot be solved exactly for
    atoms with two or more electrons. However, refined
    approximations allow one to compute wavefunctions and
    energies quite accurately.
    Orbital approximation: Approximate the wavefunction
    as a product of one electron functions or orbitals.
    (How correspondingly are we approximating the
    Hamiltonian?)
    ψ(1,2,…) = ψ1(1)ψ2(2)…..
    Each orbital may be thought of as being hydrogen-like
    with an effective nuclear charge

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    Many electron atoms
    He atom (two electrons) – electron 1 and electron 2

    Ĥ = - (ħ2/2m)12 - (Ze2/4or1) - (ħ2/2m)22 - (Ze2/4or2)


    _____________________ ______________________
    Hydrogenic electron 1 Hydrogenic electron 2

    + (e2/4or12)
    _____________
    Cannot
    Ĥ  - (ħ2/2m)12 - (Ze2/4or1) - (ħ2/2m)22 - (Ze /4orbe separated
    2) = Ĥ 1 + Ĥ 2
    2

    into parts involving one electron


    _____________________ ______________________
    Ĥ1 Ĥ2
    Orbital approximation – He atom
    The orbital approximation allows us to express the
    electronic structure of an atom in terms of its
    configuration, the list of occupied orbitals.
    For example, if one disregards the inter-electronic
    repulsion, the ground state wavefunction of He may be
    written as
    ψ(1,2) = (8/a03)1/2 e-2r1/a0 (8/a03)1/2 e-2r2/a0
    [As we have, for hydrogenic atoms, Ψ1s = (Z3/ao31/2 e-zr/ao]
    corresponding to the configuration 1s2, with the 1s
    orbital being somewhat more compact than in H.
    What about Li? (Can all 3 electrons occupy 1s orbital ?)
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    Pauli exclusion principle
    No more than two electrons may occupy a given
    orbital, and if two electrons do occupy one orbital,
    then their spins must be paired.
    The two electrons with paired spins ( have zero
    net spin angular momentum.
    This principle forms the basis of the electronic
    structure of atoms, chemical periodicity, and
    molecular structure.

    The third electron in Li must enter the n = 2 shell, but


    the 2s or the 2p? (Later)
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    Pauli principle
    When the labels of any two identical fermions (½ integer
    spin) are exchanged, the total wavefunction (including
    spin) changes sign. (ANTISYMMETRIC under
    exchange)
    Fermions ψ(2,1) = - ψ(1,2)
    When the labels of any two identical bosons (integer
    spin) are exchanged, the total wavefunction (including
    spin) remains the same. (SYMMETRIC under
    exchange).
    Bosons ψ(2,1) = ψ(1,2)
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    Orbital
    Approximation
    We construct a helium wave function as the product of
    hydrogenic orbitals with Z = 2.
    ψ(1,2) = ϕ(1)ϕ(2)

    Issue #1: an electron is fermion and fermions’ wave


    function must be antisymmetric with respect to
    interchange

    Issue #2: each electron must be either spin α or β


    Antisymmetric wavefunction
    Two electrons in same orbital (spatial wavefunction) :

    ψ(1,2) = (1) (2){spin part}


    Pauli principle: ψ(1,2) = - ψ(2,1) (MUST FOLLOW!)
    How spin part could be (for two electrons in an orbital)?

     or 

     or 

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    Antisymmetric wavefunction
    What will be the form of the wavefunction?
    ψ(1,2) = (1)(2) 
    ψ(1,2) = (1)(2) 
    ψ(1,2) = (1)(2) { +}
    ψ(1,2) = (1)(2) { - }

    It should be antisymmetric with respect to exchange of the electrons' coordinates and should be indistinguishable.
    Ψ(1,2) = (1)(2) { -}

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    Antisymmetry in the systems with
    ‘unpaired’ electrons
    What can be the form of the spatial part of the wavefunction?

    ψ(1,2) = (1)(2) or ψ(1,2) = (1)(2) ?

    To fulfill the indistinguishability of the electrons, linear


    combination of above cases may be taken.

    The total wavefunction has the form:


    ψs(1,2) = N{(1)(2)+ (1)(2)}{spin part}

    & is overall antisymmetric


    Unpaired electrons and antisymmetry
    ψs(1,2) = 0.5{(1)(2)+(1)(2)}{}

    (One combination possible: singlet)

    ψt(1,2) = 0.7071{(1)(2)-(1)(2)}

    Or

    ψt(1,2) = 0.7071{(1)(2)-(1)(2)}

    Or

    ψt(1,2) = 0.5{(1)(2)-(1)(2)}{}

    (Three degenerate combinations possible: triplet)


    Triplet will be more tightly bound and of lower energy.
    Shielding and penetration
    The third electron in Li must enter the n = 2 shell, but the 2s
    or the 2p?

    Shielding:
    In a many electron atom, each electron is shielded from
    the nucleus by the others, and to a first approximation,
    each electron may be thought of as experiencing an
    effective nuclear charge.
    The effective nuclear charge experienced by an electron
    will be determined by its probability density distribution,
    and this in turn by its wavefunction.
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    Penetration

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