V. Ilyushin1, I. Armieieva1, O. Zakharenko2, H. S. P. Müller2, F

Slides:

Advertisements

Similar presentations

+ TERAHERTZ SPECROSCOPY OF METHYLAMINE R. A. Motiyenko, L. Margulès Laboratoire PhLAM, Université Lille 1, France V.V. Ilyushin, E.A. Alekseev Insitute.

Advertisements

A fitting program for molecules with two equivalent methyl tops and C 2v point-group symmetry at equilibrium: Application to existing microwave, millimeter,

1 THz vibration-rotation-tunneling (VRT) spectroscopy of the water (D 2 O) 3 trimer : --- the 2.94THz torsional band L. K. Takahashi, W. Lin, E. Lee, F.

Microwave spectroscopy of 2-furancarboxylic acid Roman A. Motiyenko, Manuel Goubet, Laurent Margulès, Georges Wlodarczak PhLAM Laboratory, University Lille.

Hamiltonians for Floppy Molecules (as needed for FIR astronomy) A broad overview of state-of-the-art successes and failures for molecules with large amplitude.

Microwave spectrum of furfuryl alcohol Roman A. Motiyenko, Manuel Goubet, Thérèse R. Huet, Laurent Margulès, Georges Wlodarczak PhLAM Laboratory, University.

Submillimeter-wave Spectroscopy of [HCOOCH 3 ] and [H 13 COOCH 3 ] in the Torsional Excited States Atsuko Maeda, Frank C. De Lucia, and Eric Herbst Department.

WH04 NUMERICAL AND EXPERIMENTAL ASPECTS OF DATA ACQUISITION AND PROCESSING IN APPLICATION TO TEMPERATURE RESOLVED 3-D SUB-MILLIMETER SPECTROSCOPY FOR ASTROPHYSICS.

The torsional spectrum of disilane N. Moazzen-Ahmadi, University of Calgary V.-M. Horneman, University of Oulu, Finland.

Supersonic Jet Spectroscopy on TiO 2 Millimeter-wave Spectroscopy of Titanium Monoxide and Titanium Dioxide 63 rd International Symposium on Molecular.

Interaction of the hyperfine coupling and the internal rotation in methylformate M. TUDORIE, D. JEGOUSO, G. SEDES, T. R. HUET, Laboratoire de Physique.

60th OSU International Symposium on Molecular Spectroscopy TF03 The millimeter-wave rotational spectrum of lactic acid Zbigniew Kisiel, Ewa Białkowska-Jaworska,

The ground state rotational spectrum of methanol Rogier Braakman Chemistry & Chemical Engineering California Institute of Technology John C. Pearson Brian.

High-resolution threshold photoionization and photoelectron spectroscopy of propene and 2-butyne Julie M. Michaud, Konstantina Vasilatou and Frédéric Merkt.

Molecular Spectroscopy Symposium June 2011 TERAHERTZ SPECTROSCOPY OF HIGH K METHANOL TRANSITIONS John C. Pearson, Shanshan Yu, Harshal Gupta,

“Global Fit” of the high resolution infrared data of D 2 S and HDS molecules O. N. Ulenikov, E. S. Bekhtereva Physical Chemistry, ETH-Zurich, CH-8093 Zurich,

Friday, June 21, th OSU SYMPOSIUM MOLECULAR SPECTROSCOPY FB06: Cuisset & al Gas phase rovibrational spectroscopy of DMSO, Part II: « Towards a THz.

Rotational spectroscopy of two telluric compounds : vinyl- and ethyl-tellurols R.A. MOTIYENKO, L. MARGULES, M. GOUBET Laboratoire PhLAM, CNRS UMR 8523,

Precision Measurement of CO 2 Hotband Transition at 4.3  m Using a Hot Cell PEI-LING LUO, JYUN-YU TIAN, HSHAN-CHEN CHEN, Institute of Photonics Technologies,

Rotationally-Resolved Spectroscopy of the Bending Modes of Deuterated Water Dimer JACOB T. STEWART AND BENJAMIN J. MCCALL DEPARTMENT OF CHEMISTRY, UNIVERSITY.

June 21, 2012 Submillimeter Spectrum of Chloromethane: Analysis of the V 3 =1 Excited State Presented by: Alissa Fisher Auburn University and U.S. Army.

Atusko Maeda, Ivan Medvedev, Eric Herbst,

The Microwave Spectrum of Monodeuterated Acetamide CH 2 DC(=O)NH 2 I. A. Konov, a L. H. Coudert, b C. Gutle, b T. R. Huet, c L. Margulès, c R. A. Motiyenko,

1 The rotational spectrum of 13 CH 3 NH 2 up to 1 THz Roman A. Motiyenko, Laurent Margulès PhLAM, Université Lille 1 Vadim Ilyushin Institute of Radio.

Molecular Spectroscopy Symposium June 2013 Identification and Assignment of the First Excited Torsional State of CH 2 DOH Within the o 2, e.

Torsion-Rotation Program for Six-Fold Barrier Molecules Toluene MW Fit Vadim V. Ilyushin 1, Zbigniew Kisiel 2, Lech Pszczolkowski 2, Heinrich Mäder 3,

Molecular Spectroscopy Symposium June 2010 Can the Inversion-Vibration-Rotation Problem in the 4 and 2 2 States of NH 3 be solved to Experimental.

The rotational spectrum of acrylonitrile to 1.67 THz Zbigniew Kisiel, Lech Pszczółkowski Institute of Physics, Polish Academy of Sciences Brian J. Drouin,

Torsional Splitting in the Rotational Spectrum from 8 to 650 GHz of the Ground State of 1,1-Difluoroacetone L. Margulès, R. A. Motiyenko, Université de.

THz Spectroscopy of 1d-ethane: Assignment of v 18 ADAM M. DALY, BRIAN J. DROUIN, LINDA BROWN Jet Propulsion Laboratory, California Institute of Technology,

P. JANSEN, W. UBACHS, H. L. BETHLEM

Spectroscopy of the ground, first and second excited torsional states of acetaldehyde from 0.05 to 1.6 THz. Ivan Smirnov a, Eugene Alekseev a, Vadim Ilyushin.

High Resolution FIR and IR Spectroscopy of Methanol Isotopologues R.M. Lees, Li-Hong Xu Centre for Laser, Atomic and Molecular Sciences (CLAMS) Department.

SESAPS Terahertz Rotational Spectrum of the v5/2v9 Dyad of Nitric Acid * Paul Helminger, a Douglas T. Petkie, b Ivan Medvedev, b and Frank C. De.

Jun 18th rd International Symposium on Molecular Spectroscopy Microwave spectroscopy o ｆ trans-ethyl methyl ether in the torsionally excited state.

Analysis of the rotation-torsion spectrum of CH 2 DOH within the e 0, e 1, and o 1 torsional levels L. H. Coudert, a John C. Pearson, b Shanshan Yu, b.

Global Modelling of the First Three Torsional States of Methanol ( v t = 0, 1, 2, J max = 30): (CH 3 OH & CH 3 18 OH) Jonathan Fisher, Gregory Paciga,

MILLIMETRE-WAVE SPECTRUM OF ISOTOPOLOGUES OF ETHANOL FOR RADIO-ASTRONOMY Adam Walters, IRAP, Université de Toulouse, UPS-OMP-CNRS, France. Mirko Schäfer,

What is internal rotation ? The methyl group can turn relatively to the rest of the molecule and this large amplitude motion is hindered by a three-fold.

Max Planck Institute for the Structure and Dynamics of Matter

Rotational spectra of C2D4-H2S, C2D4-D2S, C2D4-HDS and 13CH2CH2-H2S complexes: Molecular symmetry group analysis Mausumi Goswami and E. Arunan Inorganic.

Analysis of bands of the 405 nm electronic transition of C3Ar

ALDO J. APPONI, JAMES J. HOY and LUCY M. ZIURYS

The microwave spectroscopy of ground state CD3SH

Isabelle Kleinera and Jon T. Hougenb

MICROWAVE AND FIR SPECTROSCOPY OF DIMETHYLSULFIDE IN THE GROUND, FIRST AND SECOND EXCITED TORSIONAL STATES V. Ilyushin1, I. Armieieva1, O. Dorovskaya1,

THE TORSIONAL FUNDAMENTAL BAND AND ROTATIONAL SPECTRA UP TO 940 GHZ OF THE GROUND, FIRST AND SECOND EXCITED TORSIONAL STATES OF ACETONE V.V. Ilyushin1,

THE MILLIMETER-WAVE SPECTRUM OF VINYL ACETATE

MILLIMETER WAVE SPECTRUM OF NITROMETHANE

Isabelle Kleinera and Jon T. Hougenb

Remeasurement* of the Microwave Spectrum of

Acetaldehyde: Into the Submillimeter

An Analysis of the Rotation Spectrum of Acetonitrile (CH3CN) in Excited Vibrational States Christopher F. Neese, James McMillian, Sarah Fortman, Frank.

THE MILLIMETER-WAVE SPECTRUM OF METHACROLEIN

The Rotational Spectrum of cis- and trans-HSSOH

A. Jabri, I. Kleiner, L. Margulès, R. Motyenko, J-C. Guillemin, E. A

62nd OSU International Symposium on Molecular Spectroscopy WG10

Rotational spectroscopy as a tool to investigate interactions between vibrational polyads in symmetric top molecules: low-lying states v8  2 of methyl.

Fourier Transform Emission Spectroscopy of CoH and CoD

Terahertz spectroscopy of the ground state of methylamine (CH3NH2)

A. M. Daly, B. J. Drouin, J. C. Pearson, K. Sung, L. R. Brown

Synchrotron Spectroscopy and Torsional Structure of the

FTIR Synchrotron Spectroscopy of

BROADBAND MICROWAVE SPECTROSCOPY AS A TOOL TO STUDY DISPERSION INTERACTIONS IN CAMPHOR-ALCOHOL SYSTEMS MARIYAM FATIMA, CRISTÓBAL PÉREZ, MELANIE SCHNELL,

The torsional spectrum of doubly deuterated methanol CHD2OH

MOLECULES WITH A SIX-FOLD BARRIER: MICROWAVE SPECTRUM OF TOLUENE

The Rotational Spectrum and Conformational Structures of Methyl Valerate LAM NGUYEN Laboratoire Interuniversitaire des Systèmes Atmosphériques (LISA)

THE MICROWAVE SPECTRUM AND UNEXPECTED STRUCTURE OF THE BIMOLECULAR COMPLEX FORMED BETWEEN ACETYLENE AND (Z)-1-CHLORO-2-FLUOROETHYLENE Nazir D. Khan, Helen.

COMPREHENSIVE ANALYSIS OF INTERSTELLAR

Holger S. P. Müller, J. C. Pearson, S. Brünken, S. Yu,

Presentation transcript:

ADVANCES IN GLOBAL MODELLING OF METHYL MERCAPTAN CH332SH TORSION-ROTATION SPECTRUM V. Ilyushin1, I. Armieieva1, O. Zakharenko2, H. S. P. Müller2, F. Lewen2, S. Schlemmer2, L.-H. Xu3, R. M. Lees3 1 Institute of Radio Astronomy of NASU, Kharkiv, Ukraine 2 I. Physikalisches Institut, Universität zu Köln, Köln, Germany 3 Centre for Laser, Atomic and Molecular Physics, Department of Physics, University of New Brunswick, New Brunswick, Canada

Motivation =0.65 Assignments: Jmax=40, fitted microwave data Jmax=30

Motivation Current goal: increase the J coverage for CH3SH spectrum

Fits in molecules with large amplitude motions and K>2 Hamiltonian terms 4 8 11 14 17 20 J 130 640 385 895 1150 Ered cm-1 vt=0 vt=1 vt=2 vt=3 vt=4 vt=5 K=3 K=3 K=4 Acetic acid, vt=0,1, J up to 79 V. V. Ilyushin, C. P. Endres, F. Lewen, S. Schlemmer, B. J. Drouin „Submillimeter wave spectrum of acetic acid“Journal of Molecular Spectroscopy Vol. 290 pp. 31 - 41 (2013). Acetaldehyde vt=0,1,2 J up to 66 I.A. Smirnov, E.A. Alekseev, V.V. Ilyushin, L. Margulés, R.A. Motiyenko, B.J. Drouin « Spectroscopy of the ground, first and second excited torsional states of acetaldehyde from 0.05 to 1.6 THz » Journal of Molecular Spectroscopy Vol. 295 pp. 44 - 50 (2014). Toluene, m =0,1,2,+/-3 J up to 94 V. V. Ilyushin, E.A. Alekseev, Z.Kisiel, Lech Pszczółkowski, accepted by Journal of Molecular Spectroscopy

RAM36 program V. Ilyushin, Z. Kisiel, L. Pszczółkowski, H. Mäder, J. T. Hougen // J. Mol. Spectrosc. Vol. 259, pp. 26-38 (2010). The RAM36 (rho-axis-method for 3 and 6-fold barriers) code realizes the Rho-axis-method approach for the molecules with the C3v top attached to a molecular frame of Cs or C2v symmetry and having 3- or 6-fold barrier to internal rotation respectively. The program carries out a global fit of rotational transitions in several torsional states simultaneously using a two step diagonalization procedure.

Cologne (Sub-)Millimeter Spectrometer Experimental details: Frequency range: 155-250, 260-380 GHz Pressure: 40 μbar Temperature: 300 K Measurement accuracy: from 20 to 65 kHz depending on the S/N ratio Spectral resolution: Doppler limited Data acquisition rate: 20 ms/point Output power: 0.7-3 mW Frequency modulation: 47.8 kHz Frequency step: 100 kHz

Portion of the recorded spectrum of CH3SH around 327.5 GHz. experiment theory 327.5 326.25 328.75 GHz

Progress in fitting FTFIR data Li-Hong Xu et al., The J. Chem. Phys. 137, 104313 (2012) 18366 FTFIR transitions were assigned uncertainties of 0.0002 and 0.00035 cm−1 (6 and 10.5 MHz) for lower states of νt = 0 and higher, respectively. NOW # data 20150 Weight 0.00020 cm-1 rms =0.00013 cm-1

Progress in fitting MW data Li-Hong Xu et al., The J. Chem. Phys. 137, 104313 (2012) 0.687 0.89 0.065 4481 0.88 0.063 2312 1.06 0.060 1403 1.36 0.091 766 0.92 0.046 1459 1.00 0.100 1223 0.81 0.161 157 0.020 0.81 0.016 2001 Jmax = 50 24631 100

Second order parameters of the RAM Hamiltonian for CH3SH molecule Operator Parameter Valued (cm-1) current work Xu et al. pα2 F 15.04050720(92) 15.04020465(66) ½(1-cos3α) V3 441.62091 (60) 441.442236(10) ½(1-cos6α) V6 -1.5664(30) −0.572786(15) ½(1-cos9α) V9 4.471(13) 0.205603(31) ½(1-cos12α) V12 -10.336(32) - pαPa ρ 0.6518557729(19) 0.651856026(13) Pa2 ARAM 3.42788054(35) 3.42808445(84) Pb2 BRAM 0.43190947(28) 0.43201954(87) Pc2 CRAM 0.41315142(28) 0.41325076(83) {Pa,Pb} Dab −0.00737664(70) −0.0073126(59) Li-Hong Xu et al., The J. Chem. Phys. 137, 104313 (2012)

Fits in molecules with large amplitude motions and K>2 Hamiltonian terms 4 8 11 14 17 20 J 130 640 385 895 1150 Ered cm-1 vt=0 vt=1 vt=2 vt=3 vt=4 vt=5 CS stretch 708 cm-1 Reduced energies Ered for torsion-rotation levels of methyl mercaptan of E species.

Conclusions The new experimental data on the methyl mercaptan (CH3SH) spectrum were obtained in the 150 - 380 GHz range. The assignments in the vt=0,1,2 torsional states of methyl mercaptan were extended up to Jmax= 50. The analysis using RAM36 program allowed significant improvement of the quality of the fit in the vt=0,1,2 torsional states, at the expense of anomalous behavior of the torsional potential function expansion. This suggests significant perturbation from a low-lying small amplitude vibration state.

Thank you for your attention This work was done under support of the Volkswagen foundation. The assistance of Science and Technology Center in Ukraine is acknowledged (STCU partner project #P686).