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    Chapter 6

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    StefanPerendija
    This document discusses the partition functions for ideal diatomic gases. It examines the translational, rotational, vibrational, electronic, and nuclear spin partition functions. For heteronuclear diatomic molecules, the rotational partition function is derived as a sum that can be approximated as an integral at high temperatures. The total wavefunction must be symmetric or antisymmetric based on whether the nuclei are fermions or bosons. This impacts whether rotational states have even or odd angular momentum quantum numbers.

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    © All Rights Reserved
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    Chapter 6

    Uploaded by

    StefanPerendija
    33 views8 pages
    This document discusses the partition functions for ideal diatomic gases. It examines the translational, rotational, vibrational, electronic, and nuclear spin partition functions. For heteronuclear diatomic molecules, the rotational partition function is derived as a sum that can be approximated as an integral at high temperatures. The total wavefunction must be symmetric or antisymmetric based on whether the nuclei are fermions or bosons. This impacts whether rotational states have even or odd angular momentum quantum numbers.

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    © © All Rights Reserved

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    This document discusses the partition functions for ideal diatomic gases. It examines the translational, rotational, vibrational, electronic, and nuclear spin partition functions. For heteronuclear diatomic molecules, the rotational partition function is derived as a sum that can be approximated as an integral at high temperatures. The total wavefunction must be symmetric or antisymmetric based on whether the nuclei are fermions or bosons. This impacts whether rotational states have even or odd angular momentum quantum numbers.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    33 views8 pages

    Chapter 6

    Uploaded by

    StefanPerendija
    This document discusses the partition functions for ideal diatomic gases. It examines the translational, rotational, vibrational, electronic, and nuclear spin partition functions. For heteronuclear diatomic molecules, the rotational partition function is derived as a sum that can be approximated as an integral at high temperatures. The total wavefunction must be symmetric or antisymmetric based on whether the nuclei are fermions or bosons. This impacts whether rotational states have even or odd angular momentum quantum numbers.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    of 8

    CHAPTER 

    6:  Ideal Diatomic Gas

    [q q q q ]
    N

    Q ~ rot vib tr el for N indistinguishable molecules


    N!
    We will exam this more closely later
    ⎡ 2π ( m1 + m2 ) kT ⎤
    3/2

    qtr = ⎢ 2 ⎥ V
    ⎣ h ⎦

    Actually, we also need to consider nuclear spin and its


    ramifications for the rotational partition function.
    Assuming a heteronuclear diatomic
    −2θ r /T −6θ r /T
    qrot = 1 + 3e + 5e + ...
    T8π 2 IkT
    high T replace sum by ∫ → qrot = =
    θr h2
    T ⎡ 1 θr 1 ⎛ θr ⎞ ⎤
    2

    qrot (T ) = ⎢1 + + + ...⎥ The extra terms result


    θ r ⎢⎣ 3 T 15 ⎜⎝ T ⎟⎠ ⎥⎦ from doing a better sum
    → integral
    Erot = NkT + ... transformation
    CV ,rot = Nk + ...

    T
    q =
    homonuclear diatomic rot 2θ keeping only the leading term
    r

    symm # (# indistinguishable
    orientations)
    The total wave function is either antisymmetric (fermions) or symmetric
    (bosons) wrt interchange of the nuclei

    Ψtot = Ψtr Ψrot Ψvib Ψel Ψnuc

    consider H2:  nuclear spins = 1/2 (fermions)

    nuclear spin functions aβ − β a S
    αβ + β a
    αα T
    ββ

    nuclear spin          rot
    para S (‐)              J even (+)
    ortho T (+)             J   odd (‐) statistical weight 3

    nuclei of spin I 2I + 1 spin states per nucleus


    qrot ,nucl ≠ qrot qnucl

    if   θ r << T
    1 1 ∞ T
    ∑
    J even
    ≈ ∑
    J odd
    ≈
    2
    ∑
    J
    ≈
    2 ∫0
    ( 2 J + 1)e
    −θ r J ( J +1) / T
    dJ =
    2θ r

    ( 2 I + 1)
    2

    qrot ,nucl ~ = qrot (T )qnucl need θ r / T < 0.2


    2θ r to be valid 
    T
    ( 2 I + 1)
    2

    2θ r
    1 +
    In the above and following discussion, we assume a Σ g electronic state

    Half‐integral spin
    I ( 2 I + 1) antisymm nuclear spin function – even J
    ( I + 1)(2 I + 1) symm nuclear spin function – odd J
    ( I +1)( 2I +1) +I ( 2I +1) =( 2I +1)
    2

    Integral spin
    I ( 2 I + 1) antisymm nuclear spin function – odd J
    ( I + 1)(2 I + 1) symm nuclear spin function – even J

    Integral spin
    qrot ,nucl = ( I + 1)( 2 I + 1) ∑ ( 2 J + 1)e −θr J ( J +1) / T
    J even

    + I ( 2 I + 1) ∑ ( 2 J + 1) e
    θ r J ( J +1) / T

    J odd

    prefactors switched for nuclei of ½ integral spin


    H2 θ r = 85.3 ( K ) largest θr value

    qrot ,mol = ∑ ( 2 J + 1) e + 3∑ ( 2 J + 1) e
    −θ r J ( J +1) / T −θ r J ( J +1) / T

    J even J odd

    para ortho

    H2 is 100% para at T = 0
    If at equilibrium
    → 25% para at high T

    Measurements of Cv vs. T:  disagreement between theory and experiment

    problem O ↔ P interconversion slow


    so high temperature distribution locked in
    as sample is cooled

    Due to rotational
    for most homonuclear diatomics don’t have to worry levels being
    about this other than the factor of 2 symmetry #) much closer
    together
    qe = ωe1e De / kT + ωe 2 e −ε 2 / kT + ...

    De
    using free atoms as the zero
    of energy – generally need 
    only retain the 1st term

    ⎛ 2π mkT ⎞ 8π 2 IkT − β hv /2
    3/2

    ( )
    − β hv −1
    assumes no low‐lying
    q=⎜ ⎟ V e 1 − e ω e De / kT
    electronically states
    ⎝ h
    2
    ⎠ σ h2 e1

    E 5 hv hv / kT D 5 Nhv ⎛ hv ⎞
    = + + hv / kT − e E= NkT + hv / kT − ⎜ De − ⎟ N
    NkT 2 2kT ( e − 1) kT 2 e −1 ⎝ 2 ⎠
    does not contribute
    2
    Cv 5 ⎛ hv ⎞ e hv / kT
    to heat capacity
    = +⎜ ⎟
    Nk 2 ⎝ kT ⎠ ( e hv / kT − 1)2
    pV = NkT
    <E>
    S= +AnQ
    T
    S ⎡⎛ 2π mkT ⎞3/ 2 Ve5 / 2 ⎤ ⎛ 8π 2 IkTe ⎞
    = An ⎢ ⎜ ⎟ ⎥ + An ⎜ ⎟
    Nk ⎢⎣⎝ h 2
    ⎠ N ⎥⎦ ⎝ σ h 2
    ⎠

    − An (1 − e − hv / kT ) + An ωel
    hv / kT
    + hv / kT
    e −1

    μ0 ⎛ 2π mkT ⎞ 8π 2 IkT
    3/ 2
    hv
    = − An ⎜ ⎟ kT − A n +
    kT ⎝ h
    2
    ⎠ σ h2 2kT

    + An (1 − e − hv / kT ) − e − An ωel
    D
    kT

    For general polyatomic molecules we don’t have a closed
    form for the rot. energy levels.  So it would appear that we
    can’t simply extend the procedure followed for diatomics.

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