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    Stark Effect in X Y Molecules: Application To Ethylene

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    Ashwini Sawant
    This document summarizes a study on the Stark effect in ethylene (C2H4) molecules. It describes: 1) Developing a quantum model based on group theory to simulate spectra of ethylene and other D2h symmetry molecules. 2) Analyzing experimental infrared and Raman spectra to determine spectroscopic parameters of ethylene's v2 and v12 bands. 3) Extending the model and software to include the Stark effect by adding an electric field term to the Hamiltonian. 4) Calculating Stark shifts and splittings and simulating Stark spectra of the v7 and v12 bands.

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    Stark Effect in X Y Molecules: Application To Ethylene

    Uploaded by

    Ashwini Sawant
    38 views18 pages
    This document summarizes a study on the Stark effect in ethylene (C2H4) molecules. It describes: 1) Developing a quantum model based on group theory to simulate spectra of ethylene and other D2h symmetry molecules. 2) Analyzing experimental infrared and Raman spectra to determine spectroscopic parameters of ethylene's v2 and v12 bands. 3) Extending the model and software to include the Stark effect by adding an electric field term to the Hamiltonian. 4) Calculating Stark shifts and splittings and simulating Stark spectra of the v7 and v12 bands.

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    stark effect

    Original Title

    Stark_MR

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    This document summarizes a study on the Stark effect in ethylene (C2H4) molecules. It describes: 1) Developing a quantum model based on group theory to simulate spectra of ethylene and other D2h symmetry molecules. 2) Analyzing experimental infrared and Raman spectra to determine spectroscopic parameters of ethylene's v2 and v12 bands. 3) Extending the model and software to include the Stark effect by adding an electric field term to the Hamiltonian. 4) Calculating Stark shifts and splittings and simulating Stark spectra of the v7 and v12 bands.

    Copyright:

    © All Rights Reserved
    Download as PPT, PDF, TXT or read online from Scribd
    Download as ppt, pdf, or txt
    38 views18 pages

    Stark Effect in X Y Molecules: Application To Ethylene

    Uploaded by

    Ashwini Sawant
    This document summarizes a study on the Stark effect in ethylene (C2H4) molecules. It describes: 1) Developing a quantum model based on group theory to simulate spectra of ethylene and other D2h symmetry molecules. 2) Analyzing experimental infrared and Raman spectra to determine spectroscopic parameters of ethylene's v2 and v12 bands. 3) Extending the model and software to include the Stark effect by adding an electric field term to the Hamiltonian. 4) Calculating Stark shifts and splittings and simulating Stark spectra of the v7 and v12 bands.

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    © All Rights Reserved
    Download as PPT, PDF, TXT or read online from Scribd
    Download as ppt, pdf, or txt
    of 18

    Columbus, June 20--24, 2005

    Laboratoire de Physique de lUniversit de Bourgogne


    ~
    Equipe Spectroscopie et Dynamique Molculaire

    Stark Effect in X2Y4 Molecules:


    Application to Ethylene
    M. ROTGER,W. RABALLAND, V. BOUDON,
    and M. LOTE

    Columbus, June 20--24, 2005

    Objectives of this study


    The isolated ethylene molecule
    The ethylene molecule placed in an electric field:
    the Stark effect
    Conclusion and perspectives

    Columbus, June 20--24, 2005

    Objectives of this study

    Columbus, June 20--24, 2005

    Adsorption in zeolites
    Zeolites = micro-structurated porous solids
    Capture of industrial pollutants
    present in gazeous rejections
    Reversible adsorption process
    Synthesis of zeolites adapted
    to the captured molecule
    Choice of a test-molecule:
    THE ETHYLENE (C2H4)

    Columbus, June 20--24, 2005

    The isolated ethylene molecule

    Columbus, June 20--24, 2005

    Model
    Pure quantum model (developed in L.P.U.B.) based on:
    Groups theory & tensorial Algebra.
    Theory and data processing already tested on molecules
    pertaining to the C2v , C3v , C4v , Td and Oh groups.
    groups
    Same technique has been used for the D2h group.
    Tensorial formalism & operators adapted to the D2h
    symmetry.
    Software for the simulation of high-resolution spectra.

    Columbus, June 20--24, 2005

    The Molecular Hamiltonian

    V
    Vibrational
    ibrational
    R
    Rotational
    otational

    H=

    { i R ,iV }

    (R

    { iR }

    { iV }

    { i R ,iV }

    Rovibrational Hamiltonian
    - V vibrational operators are function of a+ and a operators.
    - R rotational operators are function of Jx , Jy and Jz operators.
    -t are the parameters of the model.

    Columbus, June 20--24, 2005

    Line Intensity

    Calculated spectra with D2hTDS

    Transition Frequency

    Columbus, June 20--24, 2005

    Spectrum of the v2 band of C2H4


    Fit of 23 { t }
    parameters
    - 141 data
    - Standard
    deviation (rms):
    2,3x10-3 cm-1

    We deduce:
    - v0 = 1626,176 24(61)
    - A = 4,830 12(10)
    - B = 0,994 80(10)
    - C = 0,823 457(70)
    in cm-1

    Raman spectrum recorded by D. Bermejo,


    Instituto de Estructura de la Materia, Madrid, Spain

    Columbus, June 20--24, 2005

    Spectrum of the v12 band of C2H4


    Fit of 20 { t }
    parameters
    - 822 data
    - standard
    deviation
    (rms):
    1,9x10-3 cm-1

    We deduce:
    - v0 = 1442,440 13(22)
    - A = 4,924 85(27)
    - B = 1,007 52(27)
    - C = 0,826 54(18)
    in cm-1

    IR spectrum recorded by J. Vander Auwera,


    Universit Libre de Bruxelles, Belgium

    Columbus, June 20--24, 2005

    The ethylene molecule submitted to


    an electric field: the Stark effect

    Columbus, June 20--24, 2005

    The Stark Hamiltonian


    ElectricfieldalongtheZaxis
    axis
    ofthelaboratoryframe
    StarkHamiltonian

    1
    H S H 0 ZZ EZ2
    2
    H0:zerofieldHamiltonian
    ZZ:polarisabilitytensor

    ZZ

    tS

    C R V

    iC ,iR ,iV

    iC ,iR ,iV

    iC

    iR

    iV

    C represents the direction


    cosines of the OZ
    axis
    in the (O, x y z) frame
    tS : parameters of the Stark

    Hamiltonian

    Columbus, June 20--24, 2005

    The Stark matrix


    RepresentationofcouplingsbetweensomestatesoftheStarkHamiltonian
    Shiftsandsplittings
    oftheenergylevels:
    Upper
    state

    Lower
    state

    D2hTDS software
    Stark transitions calculations

    E=0E>0

    Determination of the
    thanks to ab initio
    tS parameters of the polarisability

    Columbus, June 20--24, 2005

    Application to the Stark lines of the v7 band


    YitTsongChenandT.Oka,J.Chem.Phys.88,528290(1988)

    0
    f/kHz
    07701260
    6
    1
    v/10 cm 02642

    Shift and splitting of the rovibrational


    lines are very small !!!
    (E = 0)
    = 942,905316 cm1

    = 43.10 3 ) <
    0,000050 cm1
    (E

    J=1
    J=1
    M=0
    J=1
    |M|=1

    P(1)

    |M|=1

    42,9

    J=0
    M=0

    Ground
    State

    M=0

    E/kV.cm1

    (v7=1)
    state
    J=0

    E=0

    E>0

    We need a very good accuracy on the


    zero-field parameters for the v7 band

    Columbus, June 20--24, 2005

    Stark matrix and calculation software


    Number of non-zero matrix elements of the Stark Hamiltonian
    1,0E+07

    1,0E+06

    Isolated
    molecule:

    Molecule in an
    electric field:

    J = J

    | J J | = 0, 1, 2

    1,0E+05

    | M | = 0, , J

    1,0E+04

    Example for truncation at J = 50:


    N0 = 44 200

    1,0E+03

    NS = 8 200 000

    1,0E+02
    10

    20

    30

    40

    50

    x 185

    The Stark spectrum of the 12 band


    3.0
    2.5
    2.0
    1.5
    1.0
    0.5

    Jmax=15
    T=50K

    Zerofield
    1420

    1430

    1440
    1450
    1
    Wavenumber/cm

    1460

    1470

    Columbus, June 20--24, 2005

    Conclusion and perspectives

    Columbus, June 20--24, 2005

    Tensorial model of the molecular Hamiltonian and transition


    moments for the ethylene and all other molecules of D2h
    symmetry
    Software (D2hTDS)
    TDS for the simulation of high resolution spectra
    Analysis of experimental data in IR absorption and Raman
    spectroscopy
    Extension of the model and the programs to the Stark effect

    Extension to multipolar electric fields


    Extension of the tensorial model to confinement phenomena
    Comparison with spectra of the adsorbed molecule:

    12

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