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

Slides:



Advertisements
Similar presentations
68th OSU International Symposium on Molecular Spectroscopy TH08
Advertisements

A fitting program for molecules with two equivalent methyl tops and C 2v point-group symmetry at equilibrium: Application to existing microwave, millimeter,
Submillimeter-wave Spectroscopy of 13 C 1 -Methyl formate [H 13 COOCH 3 ] in the Ground State Atsuko Maeda, Ivan Medvedev, Eric Herbst, Frank C. De Lucia,
VI-4 JPL Catalog Upgrades: New Tools, New Formats and New Interfaces BRIAN J. DROUIN, SHANSHAN YU, JOHN C. PEARSON, Jet Propulsion Laboratory, California.
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.
Rovibronic Analysis of the State of the NO 3 Radical Henry Tran, Terrance J. Codd, Dmitry Melnik, Mourad Roudjane, and Terry A. Miller Laser Spectroscopy.
Laboratory characterization and astrophysical detection in Orion KL of higher excited states of vinyl cyanide Alicia Lopez, a Belen Tercero, a Jose Cernicharo,
Global analysis of broadband rotation and vibration-rotation spectra of sulfur dicyanide Zbigniew Kisiel, a Manfred Winnewisser, b Brenda P. Winnewisser,
Molecular Spectroscopy Symposium June 2011 ROTATIONAL SPECTROSCOPY OF HD 18 O John C. Pearson, Shanshan Yu, Harshal Gupta, and Brian J. Drouin,
60th OSU International Symposium on Molecular Spectroscopy TF03 The millimeter-wave rotational spectrum of lactic acid Zbigniew Kisiel, Ewa Białkowska-Jaworska,
Terahertz spectroscopy of excited water Shanshan Yu, John Pearson, Brian Drouin Jet Propulsion Laboratory, California Institute of Technology, USA Adam.
65th OSU International Symposium on Molecular Spectroscopy RH14.
The complete molecular geometry of salicyl aldehyde from rotational spectroscopy Orest Dorosh, Ewa Białkowska-Jaworska, Zbigniew Kisiel, Lech Pszczółkowski,
Molecular Spectroscopy Symposium June 2009 The Submillimeter Spectrum of the Ground Torsional State of CH 2 DOH J.C. PEARSON, C.S. BRAUER, S.
Structures of the cage, prism and book hexamer water clusters from multiple isotopic substitution Simon Lobsiger, Cristobal Perez, Daniel P. Zaleski, Nathan.
Observation of the weakly bound (HCl) 2 H 2 O cluster by chirped-pulse FTMW spectroscopy Zbigniew Kisiel, a Alberto Lesarri, b Justin Neill, c Matt Muckle,
The ground state rotational spectrum of methanol Rogier Braakman Chemistry & Chemical Engineering California Institute of Technology John C. Pearson Brian.
Millimeter Wave Spectrum of Iso-Propanol A. MAEDA, I. MEDVEDEV, E. HERBST and F. C. DE LUCIA Department of Physics, The Ohio State University.
Fitting the high-resolution spectroscopic data for NCNCS Zbigniew Kisiel, a Brenda P. Winnewisser, b Manfred Winnewisser, b Frank C. De Lucia, b Dennis.
Zeinab. T. Dehghani, A. Mizoguchi, H. Kanamori Department of Physics, Tokyo Institute of Technology Millimeter-Wave Spectroscopy of S 2 Cl 2 : A Candidate.
Molecular Spectroscopy Symposium June 2011 TERAHERTZ SPECTROSCOPY OF HIGH K METHANOL TRANSITIONS John C. Pearson, Shanshan Yu, Harshal Gupta,
THE PURE ROTATIONAL SPECTRA OF THE TWO LOWEST ENERGY CONFORMERS OF n-BUTYL ETHYL ETHER. B. E. Long, G. S. Grubbs II, and S. A. Cooke RH13.
The rotational spectrum of chlorine nitrate (ClONO 2 ): 6 and the 5 / 6 9 dyad Zbigniew Kisiel, Ewa Białkowska-Jaworska Institute of Physics, Polish Academy.
Chirped-pulse, FTMW spectroscopy of the lactic acid-H 2 O system Zbigniew Kisiel, a Ewa Białkowska-Jaworska, a Daniel P. Zaleski, b Justin L. Neill, b.
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 ethylamine into the THz Zbigniew Kisiel, Adam Kraśnicki Institute of Physics, Polish Academy of Sciences Ivan R. Medvedev, Christopher.
The Pure Rotational Spectrum of Pivaloyl Chloride, (CH 3 ) 3 CCOCl, between 800 and MHz. Garry S. Grubbs II, Christopher T. Dewberry, Kerry C. Etchison,
1 TORSION-ROTATION-VIBRATION EFFECTS IN THE v 20, 2 v 21, 2 v 13 AND v 21 + v 13 STATES OF CH 3 CH 2 CN Adam M. Daly, John C. Pearson, Shanshan Yu, Brian.
Molecular Spectroscopy Symposium June 2013 Modeling the Spectrum of the 2 2 and 4 States of Ammonia to Experimental Accuracy John C. Pearson.
Perturbations and vibrational energies in acrylonitrile from global analysis of its mm-wave to THz rotational spectrum Zbigniew Kisiel, a Lech Pszczółkowski,
June 16-20, rd International Symposium on Molecular Spectroscopy Direct Measurements of the Fundamental Rotational Transitions of CD and 13 CH.
61st OSU International Symposium on Molecular Spectroscopy RI12 Rotational spectrum, electric dipole moment and structure of salicyl aldehyde Zbigniew.
Atusko Maeda, Ivan Medvedev, Eric Herbst,
Analysis of interactions between excited vibrational states in the FASSST rotational spectrum of S(CN) 2 Zbigniew Kisiel, Orest Dorosh Institute of Physics,
THE ANALYSIS OF HIGH RESOLUTION SPECTRA OF ASYMMETRICALLY DEUTERATED METHOXY RADICALS CH 2 DO AND CHD 2 O (RI09) MING-WEI CHEN 1, JINJUN LIU 2, DMITRY.
HIGH RESOLUTION SPECTROSCOPY OF THE TWO LOWEST VIBRATIONAL STATES OF QUINOLINE C 9 H 7 N O. PIRALI, Z. KISIEL, M. GOUBET, S. GRUET, M.-A. MARTIN-DRUMEL,
Towards understanding quantum monodromy in quasi-symmetric molecules: FASSST rotational spectra of CH 3 NCO and CH 3 NCS Zbigniew Kisiel, a Sarah Fortman,
Molecular Spectroscopy Symposium June 2013 Identification and Assignment of the First Excited Torsional State of CH 2 DOH Within the o 2, e.
Rotational spectroscopy of newly detected atmospheric ozone depleters: CF 3 CH 2 Cl, CF 3 CCl 3, and CFClCCl 3 Zbigniew Kisiel, Ewa Białkowska-Jaworska,
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.
0 ipc kiel The rotational spectrum of the pyrrole-ammonia complex Heinrich Mäder, Christian Rensing and Friedrich Temps Institut für Physikalische Chemie.
RF11 THE JPL MILLIMETER AND SUBMILLIMETER SPECTRAL LINE CATALOG BRIAN J. DROUIN, SHANSHAN YU, JOHN C. PEARSON, Jet Propulsion Laboratory, California Institute.
FTS Studies Of The Isotopologues Of CO 2 Toward Creating A Complete And Highly Accurate Reference Standard Ben Elliott, Keeyoon Sung, Charles Miller JPL,
Update of the analysis of the pure rotational spectrum of excited vibrational states of CH 3 CH 2 CN Adam Daly, John Pearson, Shanshan Yu, Brian Drouin.
The complete rotational spectrum of CH 3 NCO up to 376 GHz Zbigniew Kisiel, a Lucie Kolesnikova, b Jose L. Alonso, b Ivan R. Medvedev, c Sarah Fortman,
Laser spectroscopy of a halocarbocation: CH 2 I + Chong Tao, Calvin Mukarakate, and Scott A. Reid Department of Chemistry, Marquette University 61 st International.
THz Spectroscopy of 1d-ethane: Assignment of v 18 ADAM M. DALY, BRIAN J. DROUIN, LINDA BROWN Jet Propulsion Laboratory, California Institute of Technology,
High Resolution FIR and IR Spectroscopy of Methanol Isotopologues R.M. Lees, Li-Hong Xu Centre for Laser, Atomic and Molecular Sciences (CLAMS) Department.
22 June st International Symposium on Molecular SpectroscopyPetkie – RE07-p1 The Rotational Spectrum of H 15 NO 3 : All States Below 1000 cm -1.
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.
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,
Microwave Spectroscopy of the Excited Vibrational States of Methanol John Pearson, Adam Daly, Jet Propulsion Laboratory, California Institute of Technology,
Analysis of the FASSST rotational spectrum of S(CN) 2 Zbigniew Kisiel, Orest Dorosh Institute of Physics, Polish Academy of Sciences Ivan R. Medvedev,
60th OSU International Symposium on Molecular Spectroscopy TA03
63rd OSU International Symposium on Molecular Spectroscopy FC01
The lowest vibrational states of urea from the rotational spectrum
NH3 measurements in the far-IR
Department of Chemistry, University of Wisconsin, Madison
Analysis of the Rotationally Resolved Spectra to the Degenerate (
Vibrational energies for acrylonitrile from
62nd OSU International Symposium on Molecular Spectroscopy WG10
Lowest vibrational states of acrylonitrile
Analysis of torsional splitting in the ν8 band of propane near 870
A. M. Daly, B. J. Drouin, J. C. Pearson, K. Sung, L. R. Brown
FTIR Synchrotron Spectroscopy of
and analysis of hyperfine structure from four quadrupolar nuclei
COMPREHENSIVE ANALYSIS OF INTERSTELLAR
Holger S. P. Müller, J. C. Pearson, S. Brünken, S. Yu,
Presentation transcript:

The rotational spectrum of acrylonitrile to 1.67 THz Zbigniew Kisiel, Lech Pszczółkowski Institute of Physics, Polish Academy of Sciences Brian J. Drouin, Carolyn S. Brauer, Shanshan Yu, John C. Pearson Jet Propulsion Laboratory, California Institute of Technology, 64th OSU International Symposium on Molecular Spectroscopy WH10

Rotational spectroscopy of acrylonitrile: review:Gerry et al., J.Phys.Chem.Ref.Data A 8, 107 (1979)  :Stolze+Sutter, Z.Naturforsch. 40a, 998 (1985) satellites:Cazzoli+Kisiel, J.Mol.Spectrosc. 130, 303 (1988) smm+struct.:Demaison et al., J.Mol.Spectrosc. 167, 400 (1994) mmw:Baskakov et al., J.Mol.Spectrosc. 179, 94 (1996) isotopic:Colmont et al., J.Mol.Spectrosc. 181, 330 (1997) first astro:Gardner+Winnewisser, Astrophys.J.. 195, L127 (1975) isotopes+astro:Muller et al., J.Mol.Spectrosc. 251, 319 (2008) Planar (C s ), relatively rigid molecule, positioned in the ab inertial plane  a = 3.815(12) D  b = 0.894(68) D

Temperature dependence of the acrylonitrile rotational spectrum:  a type transitions  b type transitions spectra measured in this work

Spectra measured with the cascaded frequency multiplication spectrometer at jpl: Broadband coverage possible well into the THz region with single scans reaching frequency spans of 100 GHz. Drouin, Mailwald, Pearson, Rev.Sci.Instr. 76, (2005)

All spectra were merged into a single file: JPL spectra/MHz Span/GHz TOTAL = Gb 500 GHz: n = 30 (6  5) 1600 GHz: n = 108 (6  2  3  3)

AABS AABS has been applied to many different types of broadband spectra: FASSST, cascaded multiplication THz, chirped pulse FTMW, Bruker FTIR..

Good visibility of high-J, a R-type transitions In this Loomis-Wood type display spectral strips are aligned on frequencies K a = 0 transitions for successive values of J. At the same time abundant spectra rapidly produce various surprises. This approach allows rapid assignment and data file construction.

Understanding of the 1.0 THz spectrum: obs. calc. b Q, K a =12←11 The majority of the visible transitions are b-type, and the strongest a-type transitions are indicated by 

Understanding of the 1.6 THz spectrum: obs. calc.

Perturbations in the lowest vibrational states in acrylonitrile: Notation used for identified perturbations, in this case between: K a = 18 in  11 =1 and K a = 22 in g.s.

Principal perturbations identified in a R-type g.s. transitions: Broadband coverage possible well into the THz region with single scans reaching frequency spans of 100 GHz. g.s. lines  11 = 1 lines Differences relative to effective single state fits are plotted.  K a = 6  K a = 4

The Hamiltonian: The g.s. and  11 =1 both belong to the A’ representation of the C s point group. These states can thus be connected by Fermi resonance and c-axis Coriolis interactions. The Hamiltonian is in 2  2 block form, where for the diagonal blocks we used Watson’s Hamiltonian in both S- and A-reduction, and vibrational energy separation  E in the  11 =1 block. The dominant off-diagonal contribution between g.s. and  11 =1 turns out to come from Fermi resonance : H F (i, j) = W F + W F J P 2 + W F K P z 2 + …, while for the c-axis Coriolis interaction it is possible to use : H c (i, j) = (G c + G c J + G c K + …) P c + (F ab + F ab J + G ab K + …) (P a P b + P b P a ) + …, although only F ab proved to be determinable. Fits and predictions were made with the SPFIT/SPCAT package of H.M.Pickett.

The fitted spectroscopic constants for g.s.   11 =1 coupling: Broadband coverage possible well into the THz region with single scans reaching frequency spans of 100 GHz.

The progress in measurements of the g.s. : Symbol size proportional to ( obs - calc )/  Red symbols for ( obs - calc ) > 3  previous: 602 lines,   fit = 94 kHz this work: 3145 lines,  fit = 143 kHz

g.s. lines can also be affected by very specific perturbations: Example here shows successive g.s. a R-type doublets for K a = 12. The two components should in all cases be degenerate, but one is shifted by perturbation with K a = 2 of  11 =1. The effect is accounted for in the fit, and note that the perturbation is for  K a =10 !

Nominal interstate transitions involving the g.s.: Transitions are the result of strong mixing between But the mixing is at J =102 and it is necessary measure the spectrum at 960 GHz ! Current work leads to  E = (2) cm -1 from the rotational spectrum To compare with  E = (18) cm -1 from the gas-phase fir spectrum (Cole+Green, J.Mol.Spectrosc. 48,246(1973). K a = 16 levels of the g.s. K a = 10 levels of  11 =1 {

Comparison of some observables with calculation: a – calculated using the 6-31G(d,p) basis, GAMESS and VIBCA.

 Extensive measurements of the rotational spectrum of acrylonitrile have been made, at frequencies up to 1.67 THz, and covering a total of more than 540 GHz.  The data set for the ground state has been extended by a factor of 5 in the number of measured lines. Coverage of quantum number values is now up to J = 129 and K a = 30.  Multiple perturbations affecting ground state lines were identified and successfully fitted in terms of coupling with  11 =1, even though that state differs in vibrational energy by (2) cm -1 (determined in this work).  The most spectacular perturbations are at J >100 and THz frequencies.  New results for all 13 C and for the 15 N species have also been obtained.  A ladder of perturbations extending from the ground state upwards has been identified, and it is possible that precise energies of all low lying vibrational states may eventually be determinable from a global analysis of the rotational spectrum.SUMMARY: