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    Chapters 13-14

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    dylanheyduk3
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    Chapters 13-14

    Uploaded by

    dylanheyduk3
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    Notes

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    2 views10 pages

    Chapters 13-14

    Uploaded by

    dylanheyduk3
    Notes

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    You are on page 1of 10

    Chapters 13-14

    Microscopic Systems (13.1, 13.4, 13.5)


    ◦ Linking microstates to macrostates
    ◦ Partition Functions (Chapter 14)
    ◦ How is energy partitioned over different energy levels?

    Jablonski diagram
    S1

    T1 v=3

    emission
    phosphoresence v=2
    abs
    v=1

    S0 v=0
    Rotational
    Electronic Vibrational

    1
    Connections to thermo
    Statistical Thermodynamics
    ◦ S = kB lnW
    ◦ W = weight or number of arrangements
    ◦ Boltzmann distribution

    Types of motion
    Translation
    ◦ Particle in a box (infinite well)
    ◦ UV-vis spectroscopy

    Rotation
    ◦ Particle on a ring/sphere
    ◦ Aromatic systems

    Vibration
    ◦ Harmonic Oscillator
    ◦ IR spectroscopy

    2
    Partition function
    Describes the statistical properties of a system in thermodynamic
    equilibrium
    ◦ Dimensionless
    ◦ Function of T and V

    Total energy = sum of all energies (translational, rotational, vibrational


    and electronic)
    ◦ E = ET + ER + EV + EE
    ◦ Partition function q = qTqRqVqE

    The ensemble
    Canonical ensemble – imaginary collection of replications of the system
    with a common temperature
    Related to Q, the canonical partition function which contains all the
    thermodynamic information
    ௤ಿ
    Q= (N indistinguishable units); Q = qN (distinguishable units)
    ே!
    Functions of Q:
    ◦ Internal energy
    ◦ Heat capacity
    ◦ Entropy
    ◦ Helmholtz and Gibbs energies
    ◦ Pressure
    ◦ Equilibrium constant

    3
    Translational Motion
    Translational
    ◦ qT
    ◦ Thermal wavelength, Λ

    Particle in a box
    Model for UV-vis spectroscopy
    Delocalized pi electron
    Translational motion
    ◦ Vibrational motion (harmonic oscillator, IR)
    ◦ Rotational motion (rigid rotor, microwave)

    4
    The model
    2 d 2 1 2
    Η=− + kx
    2m dx 2 2

    V(x) = ∞ V(x) = 0 V(x) = ∞

    Details…

    10

    5
    Rotational Motion
    2D: Particle on a ring
    ◦ Model for electron in an atom or in an aromatic ring

    3D: Particle on a sphere


    Rigid Rotor (Rotator)
    ◦ Model for microwave spectroscopy
    ◦ Rotational energy levels
    ◦ Rotational quantum number, J
    ◦ Physical selection rule: must have a permanent dipole

    11

    Rotational Motion
    Rotational
    ◦ qR
    ◦ Symmetry number, σ
    ◦ Number of indistinguishable orientations of the molecule
    ◦ Rotational temperature, θR
    ◦ Rotational constant, B
    ◦ Partition function is related to the rotational constant, which in turn is related to the
    rotational energy levels

    12

    6
    Symmetry
    Look at rotational axes
    ◦ Cn axis of rotation
    ◦ n = 360°/angle of rotation

    13

    Harmonic Oscillator
    Model for vibrational motion

    IR spectroscopy

    No gravitational force, only force on


    mass m is due to spring

    Force α displacement from origin

    Hooke’s Law: F = -kx

    14

    7
    Energy and other terms
    Total Energy = KE + PE
    PE = V(x)
    Force F = -dV/dx
    V(x) = ½ kx2
    Also, from Newton’s 2nd law: F = ma

    Angular frequency
    ◦ ω = 2πν
    ◦ Frequency (ν) = no. of vibrations per second
    Time period, τ
    ◦ ν = 1/ τ

    15

    Quantum mechanical treatment


    2 d 2 1 2
    Η=− + kx
    2m dx 2 2

    E = (v + ½)hν
    v = vibrational quantum no.
    (v = 0, 1, 2…)

    1/ 2 1/ 2
    1 k 1 k
    ν=   ν=  
    2π  m  2π  μ 

    16

    8
    Example
    Calculate the vibrational frequency of the N-H bond in a peptide linkage.
    The force constant is 700. Nm-1

    17

    Vibrational
    E = hν
    Vibrational partition function, qV
    Vibrational temperature

    18

    9
    Electronic
    Electronic partition function, qE = 1 as ΔE is large
    ◦ qE = 2 for alkali metals (s1 electron can be “spin up” or “spin down”)
    ଷ
    <ET> = kBT (equipartition theorem)
    ଶ

    19

    10

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