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 DIJON Cedex – France

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

65th Ohio State University Symposium on Molecular Spectroscopy June 21–25, Introduction

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

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

65th Ohio State University Symposium on Molecular Spectroscopy June 21–25, 2010 Lmvalue mXYZ and are rovibrational operators Stark Hamiltonian

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

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

65th Ohio State University Symposium on Molecular Spectroscopy June 21–25, the Loschmidt constant L=2, 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

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

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

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

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

65th Ohio State University Symposium on Molecular Spectroscopy June 21–25, Simulations

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

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

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

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

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