Fitting the high-resolution spectroscopic data for NCNCS Zbigniew Kisiel, a Brenda P. Winnewisser, b Manfred Winnewisser, b Frank C. De Lucia, b Dennis.

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,
High sensitivity CRDS of the a 1 ∆ g ←X 3 Σ − g band of oxygen near 1.27 μm: magnetic dipole and electric quadrupole transitions in different bands of.
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,
THE USE OF CAAARS (Computer Aided Assignment of Asymmetric Rotor Spectra ) IN THE ANALYSIS OF ROTATIONAL SPECTRA. (CAAARS) Ivan R. Medvedev, Manfred Winnewisser,
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.
Supersonic Jet Spectroscopy on TiO 2 Millimeter-wave Spectroscopy of Titanium Monoxide and Titanium Dioxide 63 rd International Symposium on Molecular.
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,
60th OSU International Symposium on Molecular Spectroscopy TF03 The millimeter-wave rotational spectrum of lactic acid Zbigniew Kisiel, Ewa Białkowska-Jaworska,
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,
Water clusters observed by chirped-pulse rotational spectroscopy: Structures and hydrogen bonding Cristobal Perez, Matt T. Muckle, Daniel P. Zaleski, Nathan.
Structures of the cage, prism and book hexamer water clusters from multiple isotopic substitution Simon Lobsiger, Cristobal Perez, Daniel P. Zaleski, Nathan.
Far-Infrared Beamline at the Canadian Light Source Brant E. Billinghurst, Tim E. May 69 th International Symposium on Molecular Spectroscopy.
Spectroscopy of NCNCS at the Canadian Light Source: the far-infrared spectrum of the ν 7 region from cm -1 (and beyond…) Dennis W. Tokaryk, Stephen.
Millimeter Wave Spectrum of Iso-Propanol A. MAEDA, I. MEDVEDEV, E. HERBST and F. C. DE LUCIA Department of Physics, The Ohio State University.
Millimeter- Wave Spectroscopy of Hydrazoic acid (HN 3 ) Brent K. Amberger, Brian J. Esselman, R. Claude Woods, Robert J. McMahon University of Wisconsin.
Molecular Spectroscopy Symposium June 2011 TERAHERTZ SPECTROSCOPY OF HIGH K METHANOL TRANSITIONS John C. Pearson, Shanshan Yu, Harshal Gupta,
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.
20 June st International Symposium on Molecular SpectroscopyPetkie – TG03-p1 The Millimeter and Submillimeter-wave Spectrum of the , 6 1.
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.
66th OSU International symposium on molecular spectroscopy
Perturbations and vibrational energies in acrylonitrile from global analysis of its mm-wave to THz rotational spectrum Zbigniew Kisiel, a Lech Pszczółkowski,
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.
3-D SUBMILLIMETER SPECTROSCOPY FOR ASTROPHYSICS AND SPECTRAL ASSIGNMENT SARAH M. FORTMAN, IVAN R. MEDVEDEV, FRANK C. DE LUCIA, Department of Physics, The.
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,
Ab Initio and Experimental Studies of the E Internal Rotor State of He-CH 3 F Kelly J. Higgins, Zhenhong Yu, and William Klemperer, Department of Chemistry.
Towards understanding quantum monodromy in quasi-symmetric molecules: FASSST rotational spectra of CH 3 NCO and CH 3 NCS Zbigniew Kisiel, a Sarah Fortman,
First results from the far-infrared beamline at the Canadian Light Source: High resolution analysis of acrolein in the 600 cm -1 region A.R.W. McKellar.
OSU International Symposium on Molecular Spectroscopy June 18 – 22, TF Infrared/Raman -- TF01, Tuesday, June 19, 2012.
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,
High resolution far-infrared spectra of thiophosgene with a synchrotron source: The 1, 5, 2 4 and bands A.R.W. McKellar National Research Council.
The rotational spectrum of acrylonitrile to 1.67 THz Zbigniew Kisiel, Lech Pszczółkowski Institute of Physics, Polish Academy of Sciences Brian J. Drouin,
Analysis of High Resolution Infrared Spectra of 1,1-Dichloroethylene in the 500 − 1000 cm −1 Range Rebecca A. Peebles, Sean A. Peebles Department of Chemistry.
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.
National Synchrotron Research Facility We conducted 4 Measuring Campaigns: May 2011, 2012, 2013, and 2014 CLS.
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,
High Resolution FIR and IR Spectroscopy of Methanol Isotopologues R.M. Lees, Li-Hong Xu Centre for Laser, Atomic and Molecular Sciences (CLAMS) Department.
FAST SCAN SUBMILLIMETER SPECTROSCOPIC TECHNIQUE (FASSST). IVAN R. MEDVEDEV, BRENDA P. WINNEWISSER, MANFRED WINNEWISSER, FRANK C. DE LUCIA, DOUGLAS T. PETKIE,
An Experimental Approach to the Prediction of Complete Millimeter and Submillimeter Spectra at Astrophysical Temperatures Ivan Medvedev and Frank C. De.
Millimeter-wave Rotational Spectrum of Deuterated Nitric Acid Rebecca A.H. Butler, Camren Coplan, Department of Physics, Pittsburg State University Doug.
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.
Rotational transitions in the and vibrational states of cis-HCOOH 7 9 Oleg I. Baskakov Department of Quantum Radiophysics, Kharkov National University.
Jun 18th rd International Symposium on Molecular Spectroscopy Microwave spectroscopy o f trans-ethyl methyl ether in the torsionally excited state.
Analysis of the FASSST rotational spectrum of S(CN) 2 Zbigniew Kisiel, Orest Dorosh Institute of Physics, Polish Academy of Sciences Ivan R. Medvedev,
Further analysis of the laboratory rotational spectrum of CH3NCO
Observing Quantum Monodromy
60th OSU International Symposium on Molecular Spectroscopy TA03
63rd OSU International Symposium on Molecular Spectroscopy FC01
International Symposium on Molecular Spectroscopy
The lowest vibrational states of urea from the rotational spectrum
Chirped pulse rotational spectroscopy
First High Resolution IR Spectra of 2,2-D2-Propane The v20 (B1) A-Type Band Near cm-1. Determination of Ground and Upper State Constants Daniel.
Department of Chemistry, University of Wisconsin, Madison
Vibrational energies for acrylonitrile from
62nd OSU International Symposium on Molecular Spectroscopy WG10
Lowest vibrational states of acrylonitrile
A. M. Daly, B. J. Drouin, J. C. Pearson, K. Sung, L. R. Brown
Synchrotron Spectroscopy and Torsional Structure of the
HIGH RESOLUTION LASER SPECTROSCOPY OF NICKEL MONOBORIDE, NiB
and analysis of hyperfine structure from four quadrupolar nuclei
COMPREHENSIVE ANALYSIS OF INTERSTELLAR
Presentation transcript:

Fitting the high-resolution spectroscopic data for NCNCS Zbigniew Kisiel, a Brenda P. Winnewisser, b Manfred Winnewisser, b Frank C. De Lucia, b Dennis W. Tokaryk, c Steven C. Ross, c Brant E. Billinghurst d a Institute of Physics, Polish Academy of Sciences, Warszawa, Poland b Department of Physics, The Ohio State University, Columbus, USA c Department of Physics, University of New Brunswick, New Brunswick, Canada d Canadian Light Source Inc., University of Saskatchewan, Saskatoon, Canada 69th International Symposium on Molecular Spectroscopy RJ15

Ground breaking studies: Winnewisser et al.Phys.Rev.Lett. 95, (2005) J.Mol.Struct. 798, 1 (2006) PCCP 12, 8158 (2010) Complete mm-wave spectrum was recorded with the FASSST technique and rotationally resolved spectra of all fundamentals recorded at the CLS (HR125 Bruker+synchrotron) The problem: even for the ground state only a small subset of the FASSST transitions was fitted with a standard asymmetric rotor Hamiltonian, and even then only at 10 . The general semi-rigid bender Hamiltonian (GSRB) provided satisfactory reproduction of the global picture but at a level greater than 10 3 . Furthermore, specific vibration-rotation perturbations have been identified but not yet made use of. Background: NCNCS is a quasilinear molecule with intriguing barrier crossing behaviour described by quantum monodromy.

Precision ? Signs ? Deviation ? A good effective fit may not be the best one: Previously reported fit to only the ground state K a =0,1,2 transition sequences (five sequences) Octic level constants required!

The SPFIT traps for unwary users: See: Crib-sheet to SPFIT/SPCAT on the PROSPE website at TRAP 1 : printed errors have a specific meaning and will normally not be standard errors TRAP 2 : the fit may not be converged TRAP 3 : derived parameter values may be constrained by too small a priori uncertainties TRAP 4 : almost all quartic centrifugals have reversed sign relative to convention TRAP 5 : improper use of the DIAG parameter affecting state labelling

Towards an improved effective fit: … fewer adjustable parameters, better deviation of fit, more reasonable values of quartic constants

Assignment using Loomis-Wood type plots: The K a =0 R-branch transition sequence for NCNC 34 S

Assignment using Loomis-Wood type plots: The K a =2 l R-branch transition sequence for NCNC 34 S

Assignment using Loomis-Wood type plots: The K a =0 R-branch transition sequence for NCN 13 CS

Spectroscopic constants for the rare isotopic species of NCNCS:

Assignment of the ground state K a =3 transitions for NCNC 34 S Prediction from the effective fit assignment

Differences between experiment and GSRB: The ground state K a =0 transition sequence NCNCS (parent) NCNC 34 S The current GSRB fit is based on reproducing constants in the J(J+1) power series approximation using a small low-J subset of eigenvalues. Advances in computer power and isotopic information allow for a considerable update.

Selective perturbations in transition sequences in different vibrational states: Fig.14, B.P.Winnewisser et al., PCCP 12, 8158 (2010)

v=0: MHz from the series v=0: MHz from the series Resonances also affect the ground state: Resonance in the K a =8 transition sequence, maximum at J”= 80,81

v=0: MHz from the series v=0: MHz from the series v=1: MHz from the series v=1: MHz from the series The matching resonance in v b =1 : The resonance is now in the K a =5 transition sequence

The neighbouring K a =6 sequence for the ground state: v b =2, K a =4

 The effective fit of the rotational Hamiltonian has been improved and reproduces the five lowest K a transition frequencies to within experimental accuracy (but with no predictive properties outside this data range)  The effective constants allowed making precise predictions of spectra for the singly substituted isotopic species of NCNCS  The spectra of the three strongest naturally abundant isotopic species of NCNCS: 34 S, 13 C 1, 13 C 2 have all been assigned and validity of the derived spectroscopic constants confirmed  The prediction of isotopic species with GSRB is found to be at a very systematic deviation relative to experiment, and may be refined with a suitable correction  The recent observation of pure rotational b-type transitions with the Bruker HR125 interferometer at the CLS provides a much stronger constraint on the effective fit. Reliable estimate of v b should now be possible from perturbations in the pure rotation spectrum (providing a double check and complementing the results from the vibration-rotation spectrum…) CONCLUSIONS: