International Symposium on Molecular Spectroscopy High-resolution stimulated Raman spectroscopy and analysis of line positions and assignments for the ν2 and ν3 bands of 13C2H4 A. ALKADROU, M. ROTGER, GSMA, UMR 7331 CNRS-Université de Reims, Champagne-Ardenne, Moulin de la Housse, B.P. 1039, Cases 16-17, F-51687 Reims D.Bermejo, J. L. Doménech, Instituto de Estructura de la Materia, CSIC, Serrano 123, 28006 Madrid, Spain V. BOUDON, Laboratoire Interdisciplinaire Carnot de Bourgogne, UMR 6303 CNRS-Université de Bourgogne, 9 avenue Alain Savary, BP 47870, F-21078 Dijon Cedex, France International Symposium on Molecular Spectroscopy 71ST MEETING – JUNE 20-24, 2016 – CHAMPAIGN-URBANA, ILLINOIS

CONTENTS Introduction & general ideas Raman spectroscopy at IEM-CSIC Theoretical model Analysis and Discussion Conclusion

Why ethylene ? Effects atmospheric chemistry, global climate Effects the concentration of O3 (absorbs > 97 % UV ) in Earth's atmosphere In the Earth: C2H4 is a tropospheric pollutant produced by biomass fires, plant life and the chemical industry. In the atmosphere: Photochemical reactions with O2, N, OH and O3 produce CH2O, N2O and CH2O2 C2H4 is detected in the atmosphere of outer solar system bodies  Jupiter, Saturn, Neptun, Titan, GJ 436b   From ethylene to plastics & other uses (156 Mt de C2H4 en 2013)  Polyethylene, Polypropylene, Polyester, Nylon, Teflon, polymer…  Antifreeze solutions and solvents

Vibrational Modes of Ethylene (D2h symmetry) ν1(Ag) ν2(Ag) ν3(Ag) ν4(Au) ν5(B2g) ν6(B2g) 3026 cm-1 1623 cm-1 1343.3 cm-1 1025.6 cm-1 3083.4 cm-1 1225.4 cm-1 ν7(B2u) ν8(B3g) ν9(B3u) ν10(B3u) ν11(B1u) ν12(B1u) 948.8 cm-1 939.9 cm-1 3104 cm-1 825.9 cm-1 2988.6 cm-1 1442.4 cm-1 IR active Raman active Inactive

Recorded spectra of 13C2H4 in the regions of v2 and v3 Raman active Raman spectra recorded by inverse Raman spectroscopy in the Institute of the Structure of Matter, Madrid Resolution at 0.002 cm-1 Table 1. Experimental conditions, adapted to the ν2 and ν3 Bands of 13C2H4 ♯ Ptot/hPa T/K Band S1 7.00 296 ν2 S2 3.00 145 S3 ν3 S4

Tensorial formalism and analysis Polyad structure Pn Systematic tensorial development P2 P1 Effective Hamiltonian and vibrational extrapolation P0

Analysis of the ν2 band of 13C2H4 Molecule 13C2H4 12C2H*4 Band center 1585.19 1626.17 Region (cm-1) 1580.0 – 1585.2 1623.4 – 1626.4 * 12C2H4 reported by A Ballandras et al, J. Raman Spectrosc 2013,44,1033

Analysis of the ν3 band of 13C2H4 Molecule 13C2H4 12C2H*4 Band center 1329.51 1343.30 Region (cm-1) 1329.5 – 1330.5 1343.3 – 1345.0 * v2 in interaction with v6 reported by A Ballandras et al, J. Raman Spectrosc 2013,44,1033

Effective Hamiltonian parameters for the v2 band of 13C2H4

Effective Hamiltonian parameters for the v3 band of 13C2H4

Conclusion Raman recorded spectra of 13C2H4 in the region of Raman active of v2 and v3 Inverse Raman spectroscopy in the Institute of the Structure of Matter, Madrid The D2h Top Data System 103 Raman line positions assigned to ν2 band,  RMS of 0.54×10-3 cm-1 , 14/20 Hamiltonian Parameters fitted 51 Raman line positions assigned to ν3 bands  RMS of 0.36 × 10-3 cm-1 , 10/20 Hamiltonian Parameters fitted Provide global analysis and modeling of the 13C2H4 from 3 to 10 μm

High-resolution stimulated Raman spectroscopy and analysis of line positions and assignments for the ν2 and ν3 bands of 13C2H4

Acknowledgement International Symposium on Molecular Spectroscopy A. ALKADROU, M. ROTGER, GSMA, UMR 7331 CNRS-Université de Reims, Champagne-Ardenne, Moulin de la Housse, B.P. 1039, Cases 16-17, F-51687 Reims D.Bermejo, J. L. Doménech, Instituto de Estructura de la Materia, CSIC, Serrano 123, 28006 Madrid, Spain V. BOUDON, Laboratoire Interdisciplinaire Carnot de Bourgogne, UMR 6303 CNRS-Université de Bourgogne, 9 avenue Alain Savary, BP 47870, F-21078 Dijon Cedex, France International Symposium on Molecular Spectroscopy 71ST MEETING – JUNE 20-24, 2016 – CHAMPAIGN-URBANA, ILLINOIS