1. 65th Ohio State University Symposium on Molecular Spectroscopy June 21–25, 2010 Stark spectrum simulation of X 2 Y 4 asymmetric molecules: application to ethylene in a MFI-type host zeolite M. Sanzharov, M. Rotger, V. Boudon, M. Loëte, N. Zvereva-Loëte, A. Ballandras, G. Weber Stark spectrum simulation of X 2 Y 4 asymmetric molecules: application to ethylene in a MFI-type host zeolite M. Sanzharov, M. Rotger, V. Boudon, M. Loëte, N. Zvereva-Loëte, A. Ballandras, G. Weber Laboratoire interdisciplinaire Carnot de Bourgogne, UMR 5209 CNRS - Université de Bourgogne 9 av. A. Savary, BP 47870, F-21078 DIJON Cedex – France

2. 65th Ohio State University Symposium on Molecular Spectroscopy June 21–25, 2010Contents 1. Introduction 2. Theoretical model 3. Experimental details 4. Simulations 5. Conclusion and perspectives

3. 65th Ohio State University Symposium on Molecular Spectroscopy June 21–25, 2010 1.Introduction

4. 65th Ohio State University Symposium on Molecular Spectroscopy June 21–25, 2010 Porosity of MFI zeolite Adsorption of ethylene on highly siliceous ZSM-5 zeolite Approaches  ab initio calculations of ethylene in zeolithe  ab initio calculations for ethylene-ethylene complex  Stark calculations

5. 65th Ohio State University Symposium on Molecular Spectroscopy June 21–25, 2010 2. Theoretical model

6. 65th Ohio State University Symposium on Molecular Spectroscopy June 21–25, 2010 Lmvalue 00 2-20 20 20 210 220 mXYZ 10 0001 0 and are rovibrational operators Stark Hamiltonian

7. 65th Ohio State University Symposium on Molecular Spectroscopy June 21–25, 2010 Initial Hamiltonian Effective Hamiltonian t – model parameters V – vibrational operator R - rotational operator Rovibrational coupled basis The zero-field Hamiltonian operator

8. 65th Ohio State University Symposium on Molecular Spectroscopy June 21–25, 2010 Selection rules Stark matrix Evolution of the energy levels with the rise of an electric field

9. 65th Ohio State University Symposium on Molecular Spectroscopy June 21–25, 2010 -the Loschmidt constant L=2,686754.10 19 cm -1 -the reference temperature T 0 =273,15 K -the temperature of gas T in K -the partition function of system Q(T) Stark electric dipole moment intensities

10. 65th Ohio State University Symposium on Molecular Spectroscopy June 21–25, 2010 The truncation of Stark matrix problem (I)

11. 65th Ohio State University Symposium on Molecular Spectroscopy June 21–25, 2010 The truncation of Stark matrix problem (II)

12. 65th Ohio State University Symposium on Molecular Spectroscopy June 21–25, 2010 3. Experimental details

13. 65th Ohio State University Symposium on Molecular Spectroscopy June 21–25, 2010 In situ experimental set-up UHV magnetic sample transporter Baratron pressure gauges (10 et 1000 hPa) Infrared cell Input of dry nitrogen gas Heat chamber Gas supply & high vacuum Gas and vacuum valves

14. 65th Ohio State University Symposium on Molecular Spectroscopy June 21–25, 2010 4. Simulations

15. 65th Ohio State University Symposium on Molecular Spectroscopy June 21–25, 2010 Spectrum simulation of the 12 band with a zero-field

16. 65th Ohio State University Symposium on Molecular Spectroscopy June 21–25, 2010 High resolution Stark spectrum

17. 65th Ohio State University Symposium on Molecular Spectroscopy June 21–25, 2010 Comparison 95,5 mbar, M max =20, Res=3 cm -1

18. 65th Ohio State University Symposium on Molecular Spectroscopy June 21–25, 2010 5. Conclusion and perspectives

19. 65th Ohio State University Symposium on Molecular Spectroscopy June 21–25, 2010 Conclusion and perspectives - For the value of an electric field E≈10 GV/m we observe a shift of the ν 12 band of Δω=8 cm -1 - The obtained results are consistant with the experimental results and the results of ab initio calculations (5.14 GV/m with PBE1PBE/6-31++(2d,2p) level of theo - The obtained results are consistant with the experimental results and the results of ab initio calculations (5.14 GV/m with PBE1PBE/6-31++(2d,2p) level of theory) - Stark spectrum simulation of the 9 and 11 bands - Stark Raman spectra - Multipole electric fields