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    GC-1(80-96)

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    王明軍

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    GC-1(80-96)

    Uploaded by

    王明軍
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    2 views17 pages

    GC-1(80-96)

    Uploaded by

    王明軍

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    © All Rights Reserved
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    Polyelectronic atoms

    Poly-electron atoms
    § Energy of electron depends on both n and l
    § The importance of shielding:
    H ® H + + e- IE = 1313 kJ/mol x 4 (a Z2/n2)
    He+ ® He2+ + e- IE = 5250 kJ/mol

    shielding from 1s e-

    But
    He ® He+ + e- IE = 2371 kJ/mol
    repulsion
    E>0
    e Z e2 Zeff < 2
    e V=-
    4 p e0 r
    attraction
    E<0 E = - 1313(Z2/n2) is no longer valid
    He2+ for poly-electron atoms.
    Poly-electron atoms
    § The solution for multi-electron systems cannot be solved
    § The H (total energy operator) contains
    § kinetic energy
    § potential energy of attraction between electron and
    nucleus
    § potential energy of repulsion between electrons
    repulsion
    E>0
    e e2
    e Vee =
    4 p e0 ree
    attraction
    E<0
    He2+
    Can not be determined

    Heisenberg uncertainty principle


    Dx • Dp ≥ h/4p
    Energies of orbitals
    § Poly-electronic atoms:
    § Same types of orbital are found as for H
    § Orbitals shrink due to increased nuclear charge (Z)
    § Energy of the same orbital is lower
    (ex. 1s e- of Li is more tightly held than in H)
    § E = F(n,l)
    1s
    2s 2p
    E 3s 3p 3d
    4s 4p 4d 4f
    5s 5p 5d 5f
    6s 6p 6d
    7s 7p
    Order of orbital energy
    § Orbital energy
    § H like atom: E depends on n
    § Others: E depends on n and l
    Penetration effect
    § The more effectively an orbital allows its electron to
    penetrate the shielding electrons, the lower is the energy of
    that orbital.

    2p
    2s

    3s 3p

    3s
    3d 3p
    Penetration effect
    § The more effectively an orbital allows its electron to
    penetrate the shielding electrons, the lower is the energy of
    that orbital.

    Penetration: 2s > 2p
    Energy: 2s < 2p
    Energy level splitting & overlap
    § E = F(n, l)
    § The energy difference between
    n and n+1 levels becomes
    smaller with higher n values.
    § The split in orbital energies
    caused by l can be comparable
    to that caused by n.
    Calculated orbital energy
    § One-electron energies of valence s and p orbitals
    13 14 15 16 17 18
    B Al Ga In Tl C Si Ge Sn Pb N P As Sb Bi O S Se Te Po F Cl Br I At Ne Ar Kr Xe Rn
    0

    p
    p
    s
    Energy s
    kJ mol-1

    -2500

    -5000
    88
    Size of Atomic Orbitals
    § The mean value of the distance of s and p
    valence orbitals from the nucleus (calculated)

    89
    Size of Atomic Orbitals
    • Size of the valence s and p orbitals of group 14

    rmax ns rmax np ½rmax np - rmax ns½


    (pm) (pm) (pm)
    C 65 64 1
    Si 95 115 20
    Ge 95 119 24
    Sn 110 137 27
    Pb 107 140 33

    For heavier elements, the significant difference in size of


    the s and p orbital leads to less efficient s-p hybridization
    and weak bonding involving an s-p hybridized state.
    90
    Relativistic effects
    § As a particle moving at a speed close to the speed
    of light, physical properties of the moving object
    changed significantly.
    – Contraction in length
    – Slowing of time dependent process
    – Increase in mass

    § In a heavy atom, electrons around the nucleus feel


    stronger attraction force and move at a speed that is
    close to the speed of light.
    Relativistic effects
    § Radial velocity of 1s electron:
    Ze 2 Ze 2 Z
    vr = = ×c =α ×c ≈ ×c
    2ε 0 h 2ε 0 hc 137
    § Mass of a moving object:
    H Hg
    mrest
    mrel = Z 1 80
    2
    1− (vr / c)
    v1s (0.007 x c) (0.58 x c)
    § Bohr radius:
    mrel 1.00003 x mrest 1.23 x mrest
    ε0h 2 h
    a0 = 2
    = ar 0.99997 x a0 0.81 x a0
    π Ze mrel 2πα cmrel
    92
    Relativistic effects
    § On atomic orbital radius
    2p
    j =3/2
    1s j =1/2

    Calculated with Z = 80 (Hg)

    2s 3s
    Relativistic effects
    § Major effects on atomic orbitals are
    – The relativistic radial contraction and energetic
    stabilization of the s and p shells (direct)
    – Spin-orbit splitting for l > 0 electrons (p, d, f,…)
    – The relativistic radial expansion and energetic
    destabilization of the (outer) d and f shells (indirect)

    § All these effects are of the same order of


    magnitude and grow roughly with Z2.
    Relativistic effects
    § Calculated relativistic contraction of the 6s orbital

    Ag Au

    5s1
    6s1
    3.7 eV 2.38 eV
    5d10
    4d10

    95
    Relativistic effects
    § Color, electron affinity and EN(2.54) of Au
    § AuI---AuI interaction (aurophilicity)
    § Negative oxidation state of Au and Pt
    ex: Cesium Auride (CsAu)
    § liquid Hg
    § Short and stable [Hg-Hg]2+ bond
    § Inert Pt(0), Au(0), Hg(0)
    96

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