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