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    Jahn-Teller Theorem: Free MCQ Tests Quality Notes

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    Sandipan Saha
    The document discusses the Jahn-Teller theorem, which states that any non-linear molecular system in a degenerate electronic state will be unstable and undergo distortion to form a system of lower symmetry and energy. It provides examples of electronic degeneracy and discusses Jahn-Teller distortion, which occurs when orbitals are asymmetrically occupied. Strong distortions occur for uneven eg orbital occupation, while weak distortions occur for uneven t2g occupation. Distortions can be Z-in or Z-out based on orbital occupation. Several examples of complexes exhibiting or not exhibiting Jahn-Teller distortion are analyzed.

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    Jahn-Teller Theorem: Free MCQ Tests Quality Notes

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    Sandipan Saha
    556 views14 pages
    The document discusses the Jahn-Teller theorem, which states that any non-linear molecular system in a degenerate electronic state will be unstable and undergo distortion to form a system of lower symmetry and energy. It provides examples of electronic degeneracy and discusses Jahn-Teller distortion, which occurs when orbitals are asymmetrically occupied. Strong distortions occur for uneven eg orbital occupation, while weak distortions occur for uneven t2g occupation. Distortions can be Z-in or Z-out based on orbital occupation. Several examples of complexes exhibiting or not exhibiting Jahn-Teller distortion are analyzed.

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    The document discusses the Jahn-Teller theorem, which states that any non-linear molecular system in a degenerate electronic state will be unstable and undergo distortion to form a system of lower symmetry and energy. It provides examples of electronic degeneracy and discusses Jahn-Teller distortion, which occurs when orbitals are asymmetrically occupied. Strong distortions occur for uneven eg orbital occupation, while weak distortions occur for uneven t2g occupation. Distortions can be Z-in or Z-out based on orbital occupation. Several examples of complexes exhibiting or not exhibiting Jahn-Teller distortion are analyzed.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    556 views14 pages

    Jahn-Teller Theorem: Free MCQ Tests Quality Notes

    Uploaded by

    Sandipan Saha
    The document discusses the Jahn-Teller theorem, which states that any non-linear molecular system in a degenerate electronic state will be unstable and undergo distortion to form a system of lower symmetry and energy. It provides examples of electronic degeneracy and discusses Jahn-Teller distortion, which occurs when orbitals are asymmetrically occupied. Strong distortions occur for uneven eg orbital occupation, while weak distortions occur for uneven t2g occupation. Distortions can be Z-in or Z-out based on orbital occupation. Several examples of complexes exhibiting or not exhibiting Jahn-Teller distortion are analyzed.

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    Free MCQ Tests Quality notes

    In depth Solution Ask doubts

    All India Rank Exam update

    Jahn-Teller Theorem

    www.scifysolution.com February 3, 2019 0


    Jahn-Teller Theorem
    The Jahn-Teller Theorem was first published in 1937 named after
    Hermann Arthur Jahn and Edward Teller and it states that:

    "any non-linear molecular system in a degenerate electronic state will


    be unstable and will undergo distortion to form a system of lower
    symmetry and lower energy thereby removing the degeneracy"

    In above theorem we come across term electronic degeneracy, so what


    is electronic degeneracy?
    An electronically degenerate state represents to the availability of more
    than one degenerate orbitals for an electron. Here the degenerate
    orbitals are asymmetrically occupied.
    E.g. d1 configuration in octahedral symmetry is said to be electronically
    degenerate since there are three t2g orbitals with same energy
    available for the electron to occupy.

    __ __ __ __ __ __ __ __ __
    XY XZ YZ XY XZ YZ XY XZ YZ

    Electronically degenerate state of d1 configuration

    Similarly, example of non-degenerate and symmetric orbital is d3


    configuration in octahedral symmetry and that is because it is not
    possible to put two electrons in one orbital, which is against of Hund's
    rule of maximum multiplicity.

    __ __ __
    XY XZ YZ

    JAHN-TELLER DISTORTION WWW.SCIFYSOLUTION.COM


    In the electronically degenerate state, if the orbitals are asymmetrically
    occupied, get more energy. Therefore, this system tries to get rid of this
    extra energy by lowering the overall symmetry of the molecule that is
    by undergoing distortion, which is known as Jahn Teller distortion.

    Jahn Teller distortion is mostly observed in octahedral molecules. The


    Jahn Teller distortions depends on whether the orbital is filled
    asymmetrically or symmetrically and also whether it is t2g orbitals or eg
    orbital.
    Now considering the fact that d3, d8, d10, high spin d5 and low spin d6
    are symmetrically distributed there is no Jahn teller distortion
    observed in these molecules.

    d3 d8 d10 d5 (High Spin) d6 (Low Spin)


    Configuration Configuration Configuration Configuration Configuration

    __ __ __ __ __ __ __ __ __ __
    x2-y2 z2 x2-y2 z2 x2-y2 z2 x2-y2 z2 x2-y2 z2

    __ __ __ __ __ __ __ _ __ __ __ __ __ __ __
    xy xz yz xy xz yz xy xz yz xy xz yz xy xz yz

    When t2g orbitals are unevenly occupied, weak Jahn Teller distortions
    are observed, since very less energy is gained as t2g sets does not point
    directly at ligands.
    Examples- d1, d2, low spin d4 & d5, high spin d6 & d7 configurations in
    octahedral environment
    JAHN-TELLER DISTORTION WWW.SCIFYSOLUTION.COM
    d1 d2 d4 (Low Spin) d5 (Low Spin) d6 (High Spin) d7 (High Spin)
    Configuration Configuration Configuration Configuration Configuration Configuration

    __ __ __ __ __ __ __ __ __ __ __ __
    x2-y2 z2 x2-y2 z2 x2-y2 z2 x2-y2 z2 x2-y2 z2 x2-y2 z2

    __ __ __ __ __ __ __ __ __ __ __ __ __ __ __ __ __ __
    xy xz yz xy xz yz xy xz yz xy xz yz xy xz yz xy xz yz

    But when “eg” orbitals are unevenly occupied, strong Jahn Teller
    distortions are observed, since more energy is gained as “eg” orbitals
    are directly pointed to the ligands.
    Examples- d9, high spin d4, low spin d7 configuration in octahedral
    environment.

    d9 d4 (High Spin) d7 (Low Spin)


    Configuration Configuration Configuration

    __ __ __ __ __ __
    x2-y2 z2 x2-y2 z2 x2-y2 z2

    __ __ __ __ __ __ __ __ __
    xy xz yz xy xz yz xy xz yz

    JAHN-TELLER DISTORTION WWW.SCIFYSOLUTION.COM


    As we discussed above, the degeneracy of orbital’s can be removed
    by lowering the symmetry of molecule and this can be done either by
    octahedral elongation (Z-out distortion) or octahedral elongation (Z-in
    distortion)
    .

    Z-out distortion- In this type of distortion, the energies of d-orbital’s


    with z factor like dz2, dxz, dyz are lowered by elongating the bonds
    along the z-axis. This is the most preferred distortion and occurs when
    the degeneracy occurs in eg level.
    Example d4(high spin),d7 & d8(Low spin), and d9 configuration in
    octahedral symmetry
    Even though it is observed that Z-out distortion occurs mostly in eg
    Level, theoretically it is impossible to predict type of distortion in eg
    level.
    Z-in distortion- In this type of distortion, the energies of d-orbital’s
    with z factor like dz2, dxz, dyz are increased by elongating the bonds
    along the z-axis.

    JAHN-TELLER DISTORTION WWW.SCIFYSOLUTION.COM


    Example- Octahedral d1 configuration

    Z- in distortion No distortion Z- out distortion


    (Octahedral compression) (Octahedral elongation)

    Eg orbital’s

    t2g orbital’s

    JAHN-TELLER DISTORTION WWW.SCIFYSOLUTION.COM


    Solved questions from NET, SET and Gate exams on Jahn Teller
    distortion

    NET JUNE-2015

    Among the complexes K4[Cr(CN)6] (A), K4[Fe(CN)6](B), K3[Co(CN)6](C),


    K4[Mn(CN)6](D), Jahn teller distortion is expected in

    1. A, B and C 2. B, C and D

    3. A and D 4. B and C

    Ans) 3 , complex A and D

    Complex A is K4[Cr(CN)6] , the oxidation number on Cr = 4*charge on K+


    x (Oxidation no. of Cr) +(charge on cyano group)*6 =0

    4(1)+ x+(-1)6=0

    4+x-6=0

    Therefore

    x= 6-4=2

    Therefore, Cr in +2 oxidation state

    Outer electronic configuration of Chromium (Cr) is 4S1 3d5

    Outer electronic configuration of Cr +2 is 3d4

    CN ligand is strong field ligand and will result in low spin complex,
    therefore it is d4 Low spin complex.

    JAHN-TELLER DISTORTION WWW.SCIFYSOLUTION.COM


    It (complex A ) will have weak Jahn teller distortion due to asymmetric
    filled t2g orbitals

    Complex B is K4[Fe(CN)6] where oxidation no of Fe is +2

    Outer electronic configuration of Fe is 4s2, 3d6 and that of Fe+2 is 3d6

    It is d6 low spin complex

    Since t2g orbital is symmetrically distributed, no Jahn teller distortion.

    Complex C is K3[Co(CN)6] and the oxidation no of Co in the complex is


    +3

    Outer electronic configuration of Co is 4s2, 3d7 and that of Co+3 is 3d6

    JAHN-TELLER DISTORTION WWW.SCIFYSOLUTION.COM


    It is d6 low spin complex because CN is strong field ligand and thus no
    Jahn Teller distortion as incase of complex B.

    Complex D is K4[Mn(CN)6] and the oxidation state of Mn is +2

    Outer electronic configuration of Mn is 4s2, 3d5 and that of Mn+2 is 3d5

    It is d5 low spin complex because CN is strong field ligand and has weak
    Jahn Teller distortion due to asymmetrically filled t2g orbital.

    MHA SET-2018

    Jahn-Teller distortion will be exhibited by

    (A) [Mn(H2O)6]2+ (B) [Cr(H2O)6]3+


    (C) [Ni(H2O)6]2+ (D) [Cu(H2O)6]2+

    Ans) D

    JAHN-TELLER DISTORTION WWW.SCIFYSOLUTION.COM


    Complex A is [Mn(H2O)6]2+ , oxidation state of Mn is +2 and the outer
    electron of Mn+2 is 3d 5 and H2O is weak field ligand resulting in high
    spin complex, therefore complex A is d5(high spin complex).

    No Jahn Teller distortion due to symmetrically filed t2g and eg orbital’s

    Complex B is [Cr(H2O)6]3+ , oxidation state of Cr is +3 and the outer


    electron of Cr+3 is 3d3

    No Jahn Teller distortion due to symmetrically filed t2g orbital’s.

    Complex C is [Ni(H2O)6]2+ , oxidation state of Ni is +2 and the outer


    electron of Ni+2 is 3d8

    JAHN-TELLER DISTORTION WWW.SCIFYSOLUTION.COM


    No Jahn Teller distortion due to symmetrically filed t2g and eg orbital’s

    Complex D is [Cu(H2O)6]2+ , oxidation state of Cu is +2 and the outer


    electron of Cu+2 is 3d 9

    Complex D will exhibit strong Jahn teller distortion due to


    asymmetrically filled eg orbital’s

    IIT JAM-2017

    Jahn-Taller distortion is/are observed in octahedral complexes with d-


    electron configuration of :
    JAHN-TELLER DISTORTION WWW.SCIFYSOLUTION.COM
    (A) d5-high spin (B) d5-low spin
    (C) d6-high spin (D) d6-low spin

    Ans) B and C

    A is d5 high spin complex

    No Jahn Teller distortion due to symmetrically filed t2g and eg orbital’s

    B is d5 low spin complex

    Jahn Teller distortion due to asymmetrically filed t2g orbital’s

    C is d6 high spin complex.

    JAHN-TELLER DISTORTION WWW.SCIFYSOLUTION.COM


    Jahn Teller distortion due to asymmetrically filed t2g orbital’s

    D is d6 low spin complex.

    No Jahn Teller distortion due to symmetrically filed t2g orbital’s

    JAHN-TELLER DISTORTION WWW.SCIFYSOLUTION.COM


    JAHN-TELLER DISTORTION WWW.SCIFYSOLUTION.COM

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