Institute of Physics, Polish Academy of Sciences
Who we are
What do we do
Our hardware
Our software
Some previous work
  

      

This laboratory is called  ON2.3 - Millimetre and Submillimetre Spectroscopy. 

Our main research activity is rotational spectroscopy of small molecules and intermolecular complexes at frequencies from 2 to ca 500 GHz.

      

Mm-wave rotational spectrum of pyrimidine
     

Staff and PhD students
      
Prof. dr hab. Zbigniew KISIEL kisiel@ifpan.edu.pl
 
Dr Ewa BIALKOWSKA-JAWORSKA
Mgr Orest DOROSH
Mgr Adam KRASNICKI
Mgr Lech PSZCZOLKOWSKI  
Jerzy KOSARZEWSKI
 
Fax:  +48-22-8430926
Phone:  +48-22-8436601 tone 3227,2741

      

Geometry of the weakly bound cyclic trimer (H2O)2HCl
  Research
         Our research is mainly concerned with recording and analysis of pure rotational spectra of molecules and of weakly bound intermolecular complexes.  These studies are carried out in the gas-phase and the spectra arise from quantised end-over-end rotation of molecules. 

       Analysis of rotational spectra allows highly precise determination of the geometry, of the electric dipole moment, and of inter- and intra-molecular interactions in the studied species.  An important feature of the derived molecular information is that it is for isolated molecules and has traditionally provided a benchmark for ab initio quantum chemistry calculations.

      

       There are two principal lines of our research:

      

  Rotational spectroscopy of small molecules, including species of atmospheric and astrophysical interest:
         Recent studies include those of:
             
Halon BCF - extinguishant withdrawn to protect the ozone layer CBrClF2 Freon-22 - refrigerant  CHF2Cl Methylene chloride  CH2Cl2
Methylene iodide CH2I2 1,1-Dichloroethylene H2C=CCl2 Trichloroethylene  Cl2C=CHCl
Chloroacrylonitrile H2C=CClCN 1,1,1-trichloroethane Cl3CCH3 1,1,1-trichloroethane HCCl3
Backbone molecule for DNA bases Pyrimidine Interesting pre-fullerene cage molecule, C10H15F 1-F-adamantane Quinoline and Isoquinoline, C9H7N Diethyl ether
Carrier of the model six-fold barrier to internal rotation Benzene derivatives
 Well known early anaesthetic Quinoline /  Isoquinoline Carrier of the model six-fold barrier to internal rotation Acetone
F, Cl, Br, I-benzene Acetic acid
 C10 H16 O Lactic acid
 C10 H16 O Pyruvic acid
C10 H16 O Camphor C10 H16 O 1,2-benzodioxole
 Tertiary butyl molecules with X = F, Cl, Br, I, CN, and NC t-BuX

       Their aim has been to determine new molecular information as well as spectroscopic constants for use in environmental (i.e. atmospheric and astrophysical) applications.

                       

  Rotational spectroscopy of intermolecular complexes:
 

       Recent examples:

             
  H2O...HCl   (H2O)2HCl   (H2O...HCl)...Ar
  36Ar...HCl   Ar2...HBr van-der-Waals dimers and trimers (n=2,3) with X=F,Cl,Br  ArnHX
  N2...HCl   N2...HBr   Pyrimidine...H2O
  (H2O)2HBr Ar...HC3N    

       The goal of these studies is to improve the understanding of the nature of the intermolecular interaction. They allow precise determination of the geometry, dipole moment, nuclear quadrupole splitting constants, and of the effect of the shape of the intermolecular potential on the measured spectroscopic observables.

            

  Equipment
        Most of our experimental studies are performed on equipment constructed in our laboratory, which currently consists of two complementary spectrometers:

      

  A broadband millimetre wave (MMW) spectrometer:
             The spectrometer is based on Istok-type high-frequency Backward Wave Oscillators. The sources are phase locked, in two PLL loops, to a 3 GHz synthesiser. Measurements are made in transmission using source modulation, second derivative detection, and GaAs or InSb detectors. The preferred operating range is 150-350 GHz, although the available coverage is from <100 to >500 GHz. The picture shows the free-space optics of the higher frequency PLL loop, which locks the source to a K-band harmonic. 

      

  A cavity Fourier Transform Microwave (FTMW) spectrometer
         This spectrometer allows recording of sub-Doppler spectra of supersonically cooled samples.  The operating range is 2-18.5 GHz and electrodes for Stark measurements are available.  It is possible to measure spectra in standard supersonic expansion through a standard circular pulsed nozzle, with a heated nozzle, and with a nozzle equipped with electric discharge. The white high-vacuum cavity contains a confocal Fabry-Perot microwave resonator with 50 cm diameter mirrors.

      

  Programs for ROtational SPEctroscopy
        

       The processing and interpretation of spectroscopic data is often a computationally intensive task and the availability of suitable programs is crucial to the efficiency of such studies.  For this reason we maintain a database of computer programs dealing with various aspects of the rotational spectroscopy problem. The PROSPE database contains extensively tested, well documented programs written both in this laboratory and elsewhere.

      

      

 
 
  Some recent studies and publications
 
 

Recent PhD Theses

    
  • Beata Agnieszka Pietrewicz: "Spektroskopia rotacyjna wybranych czasteczek i kompleksów miedzyczasteczkowych w naddzwiekowej wiazce molekularnej", IFPAN, 2003.Reprint
  • Oleksandr Desyatnyk: "Wyznaczanie struktur i momentów dipolowych czasteczek metoda spektroskopii rotacyjnej", IFPAN, 2005.Reprint

   

Weakly bound intermolecular complexes

      

  • (H2O)2...HCl:

    Z.Kisiel, E.Bialkowska-Jaworska, L.Pszczolkowski, A.Milet, C.Struniewicz, R.Moszynski, and J.Sadlej, "Structure and properties of the weakly bound trimer (H2O)2...HCl observed by rotational spectroscopy", J.Chem.Phys. 112, 5767-5776 (2000).

    Z.Kisiel, J.Kosarzewski, B.A.Pietrewicz, and L.Pszczolkowski, "Electric dipole moments of the cyclic trimers (H2O)2...HCl and (H2O)2...HBr from Stark effects in their rotational spectra", Chem.Phys.Lett. 325, 523-530 (2000).

  • (H2O)2...HBr:

    Z.Kisiel, B.A.Pietrewicz, O.Desyatnyk, L.Pszczolkowski, I.Struniewicz, and J.Sadlej, "Structure and properties of the weakly bound cyclic trimer (H2O)2...HBr observed by rotational spectroscopy", J.Chem.Phys. 119, 5907-5917 (2003).

    Z.Kisiel, J.Kosarzewski, B.A.Pietrewicz, and L.Pszczolkowski, "Electric dipole moments of the cyclic trimers (H2O)2...HCl and (H2O)2...HBr from Stark effects in their rotational spectra", Chem.Phys.Lett. 325, 523-530 (2000).

  • H2O...HCl:

    Z.Kisiel, B.A.Pietrewicz, P.W.Fowler, A.C.Legon, and E.Steiner, "Rotational spectra of the less common isotopomers, electric dipole moment and the double minimum inversion potential of H2O...HCl", J.Phys.Chem.A 104, 6970-6978 (2000).

    see also: Z.Kisiel, "Least-squares mass-dependence molecular structures for selected weakly-bound intermolecular complexes", J.Mol.Spectrosc. 218, 58-67 (2003).

  • Ar...HCl: Z.Kisiel and L.Pszczolkowski, "Rotational spectrum and spectroscopic constants of 36Ar...H35Cl and 40Ar...HCl", Chem.Phys.Lett. 291,190-196 (1998).
  • Arn...HX, n=2,3, X=F, Cl, Br: Z.Kisiel, E.Bialkowska-Jaworska, and L.Pszczolkowski, "The experimental electric dipole moments of the ArnHX van der Waals clusters", Chem.Phys.Lett. 333,381-386 (2001).
  • Pyrimidine...H2O: S.Melandri, M.E.Sanz, W.Caminati, P.G.Favero, and Z.Kisiel, "The hydrogen bond between water and aromatic bases of biological interest: an experimental and theoretical study of the 1:1 complex of pyrimidine with water", J.Amer.Chem.Soc. 120, 11504-11509 (1998).
  • N2...HCl: Z.Kisiel and L.Pszczolkowski, P.W.Fowler, and A.C.Legon, "Rotational spectrum of 14N2...H35Cl and 14N2...H37Cl: electric field gradients at the nitrogen nuclei", Chem.Phys.Lett. 276, 202-209 (1997).
  • N2...HBr: Z.Kisiel, B.A.Pietrewicz, and L.Pszczolkowski, "Rotational spectrum of the most abundant isotopomer of the van der Waals dimer N2...HBr", Acta Physica Polonica A. 101, 231-242 (2002).Reprint
  • Ar2...HBr:

    Z.Kisiel, B.A.Pietrewicz, and L.Pszczolkowski, "The observation and characterisation by rotational spectroscopy of the weakly bound trimer Ar2HBr", J.Chem.Phys. 117, 8248-8255 (2002).

    Z.Kisiel, E.Bialkowska-Jaworska, and L.Pszczolkowski, Chem.Phys.Lett. 333,381-386 (2001) - dipole moment measurement only.

  • (H2O...HCl)...Ar: ms. in prep.
  • Ar...HCCCN: O.Desyatnyk, J.Kosarzewski, Z.Kisiel, "Observation and properties of the van der Waals dimer Ar...HCCCN produced in electrical discharge", Acta Physica Polonica A 104, 415-424 (2003).Reprint

     

Isolated molecules

   

Trichloroethylene, Cl2C=CHCl (a well known solvent):

  • Z.Kisiel, E.Bialkowska-Jaworska, and L.Pszczolkowski, "Nuclear quadrupole coupling in Cl2C=CHCl and Cl2C=CH2; "Evidence for systematic differences in orientation between internuclear and field gradient axes for terminal quadrupolar nuclei", J.Chem.Phys. 109, 10263-10272 (1998).
  • Z.Kisiel and L.Pszczolkowski, "Assignment and analysis of the mm-wave rotational spectrum of trichloroethylene: observation of a new, extended b.R-band and an overview of high-J, R-type bands", J.Mol.Spectrosc. 177, 125-137 (1996).

1,1,1-trichloroethane, Cl3CCH3 (another popular industrial solvent):

  • L.Dore and Z.Kisiel, "Nuclear quadrupole coupling in 1,1,1-Trichloroethane: Inertial and principal tensors for 35Cl and 37Cl", J.Mol.Spectrosc. 189, 228-234 (1998).
  • Z.Kisiel and L.Pszczolkowski, "Millimeter wave rotational spectra of the 37Cl species of 1,1,1,-trichloroethane" J.Mol.Spectrosc. 181, 48-55 (1997).
  • G.Cazzoli, G.Cotti, L.Dore, and Z.Kisiel, "The high frequency rotational spectrum of 1,1,1-trichloroethane and the observation of K=3 splitting", J.Mol.Spectrosc. 174, 425-432 (1995).

Chlorobromodifluoromethane, CBrClF2 (the popular fillant for fire extinguishers, removed from use following concerns over the well-being of the ozone layer):

  • Z.Kisiel, E.Bialkowska-Jaworska, and L.Pszczolkowski, "Nuclear quadrupole coupling in Cl2C=CHCl and Cl2C=CH2; Evidence for systematic differences in orientation between internuclear and field gradient axes for terminal quadrupolar nuclei", J.Chem.Phys. 109, 10263-10272 (1998).
  • Z.Kisiel and L.Pszczolkowski, "Assignment and analysis of the mm-wave rotational spectrum of trichloroethylene: observation of a new, extended b.R-band and an overview of high-J, R-type bands", J.Mol.Spectrosc. 177, 125-137 (1996).

Chlorofluoromethane, CHF2Cl (the freon CFC-22, widely used as an intermediate replacement for the CFC-11 and CFC-12 refrigerants which were relegated from use due to adverse effect on the ozone layer):

  • Z.Kisiel, J.L.Alonso, S.Blanco, G.Cazzoli, J.M.Colmont, G.Cotti, G.Graner, J.C.Lopez, I.Merke, and L.Pszczolkowski, "Spectroscopic constants for HCFC-22 from rotational and high-resolution vibration spectra: CHF237Cl and 13CHF235Cl isotopomers", J.Mol.Spectrosc. 184, 150-155 (1997).
  • Z.Kisiel, L.Pszczolkowski, G.Cazzoli, and G.Cotti, "The millimeter-wave rotational spectrum and Coriolis interaction in the two lowest excited vibrational states of CHClF2", J.Mol.Spectrosc. 173, 477-487 (1995).
  • G.Klatt, G.Graner, S.Klee, G.Mellau, Z.Kisiel, L.Pszczolkowski, J.L.Alonso, and J.C.Lopez, "Analysis of the high-resolution FT-IR and millimeter-wave spectra of the v5=1 state of CHF2Cl", J.Mol.Spectrosc. 178, 108-112 (1996).

Methylene iodide, CH2I2 (a rather taxing problem for rotational spectroscopy):

  • Z.Kisiel, E.Bialkowska-Jaworska, L.Pszczolkowski, "The <ICI bending satellites in the millimeter-wave rotational spectra of CH2I2 and CD2I2", J.Mol.Spectrosc. 199, 5-12 (2000).
  • Z.Kisiel, L.Pszczolkowski, L.B.Favero, and W.Caminati, "An isotopomer of the first molecule containing two iodine nuclei investigated by microwave spectroscopy", J.Mol.Spectrosc. 189, 283-290 (1998).
  • Z.Kisiel, L.Pszczolkowski, W.Caminati, and P.G.Favero, "First assignment of the rotational spectrum of a molecule containing two iodine nuclei: spectroscopic constants and structure of CH2I2", J.Chem.Phys. 105, 1778-1785 (1996).

Diethyl ether, C2H5OC2H5 (the classical anaesthetic):

  • I.Medvedev, M.Winnewisser, F.C.De Lucia, E.Herbst, E.Yi, L.P.Leong, R.P.A.Bettens, E.Bialkowska-Jaworska, O.Desyatnyk, L.Pszczolkowski, Z.Kisiel, "The millimeter- and submillimeter-wave spectrum of the trans-trans conformer of diethyl ether C2H5OC2H5", Astrophys.J.Suppl.Series 148, 593-597 (2003).
  • I.Medvedev, M.Winnewisser, F.C.De Lucia, E.Herbst, E.Bialkowska-Jaworska, L.Pszczolkowski, Z.Kisiel, "The millimeter- and submillimeter-wave spectrum of the trans-gauche conformer of diethyl ether", J.Mol.Spectrosc. 228, 314-328 (2004).
  • Z.Kisiel, L.Pszczolkowski, I.R.Medvedev, M.Winnewisser, F.C.De Lucia, E.Herbst, "Rotational spectrum of trans-trans diethyl ether in the ground and three excited vibrational states", J.Mol.Spectrosc. 233, 231-243 (2005).

Chlorine nitrate, ClONO2 (important stratospheric molecule):

  • R.A.H.Butler, D.T.Petkie, P.Helminger, F.C.De Lucia, Z.Kisiel, "The rotational spectrum of chlorine nitrate (ClONO2): The v5/v6v9 dyad", J.Mol.Spectrosc. 243, 1-9 (2007).
  • R.A.H.Butler, D.T.Petkie, P.Helminger, F.C.De Lucia, E.Bialkowska-Jaworska, Z.Kisiel, "The rotational spectrum of chlorine nitrate (CLONO2): The v6 vibratinal state", J.Mol.Spectrosc. 244, 113-116 (2007).

Pyrimidine (nucleic acid backbone molecule):

  • Z.Kisiel, L.Pszczolkowski, J.C.Lopez, J.L.Alonso, A.Maris, and W.Caminati, "Investigation of the rotational spectrum of pyrimidine from 3 to 337 GHz: Molecular structure, nuclear quadrupole coupling, and vibrational satellites", J.Mol.Spectrosc., 195,332-339(1999).
  • Y-J.Kuan, C-H.Yan, S.B.Charnley, Z.Kisiel, P.Ehrenfreund, H-C.Huang, "A search for interstellar pyrimidine", Mon.Not.R.Astron.Soc. 345,650-656(2003).
  • Z.Peeters, O.Botta, S.B.Charnley, Z.Kisiel, Y.-J.Kuan, P.Ehrenfreund, "Formation and photostability of N-heterocycles in space - I. The effect of nitrogen on the photostability of small aromatic molecules", Astron. & Astrophys. 433, 583-590 (2005).

Various singly substituted benzene derivatives:

  • Toluene: Z.Kisiel, E.Bialkowska-Jaworska, L.Pszczolkowski, H.Mader, "Ground state rotational spectrum of toluene", J.Mol.Spectrosc., 227, 109-113 (2004).
  • Fluorobenzene: Z.Kisiel, E.Bialkowska-Jaworska, L.Pszczolkowski, "The millimeter-wave rotational spectrum of fluorobenzene", J.Mol.Spectrosc. 232, 47-54 (2005).
  • Chlorobenzene, Bromobenzene, Iodobenzene: O.Dorosh, E.Bialkowska-Jaworska, Z.Kisiel, L.Pszczolkowski, "New measurements and global analysis of rotational spectra of Cl-, Br- , and I-benzene: Spectroscopic constants and electric dipole moments", J.Mol.Spectrosc. 246, 228-232 (2007).
  • Anisole and Benzaldehyde: O.Desyatnyk, L.Pszczolkowski, S.Thorwirth, T.M.Krygowski, Z.Kisiel, "The rotational spectra, electric dipole moments and molecular structures of anisole and benzaldehyde", Phys.Chem.Chem.Phys. 7, 1708-1715 (2005); correction Phys.Chem.Chem.Phys. 7, 2080 (2005).

Some other molecules recently studied with either the MMW or FTMW spectrometers in Warsaw (or both):

  • H2C=CClCN: Z.Kisiel and L.Pszczolkowski, "Nuclear quadrupole coupling in 2-chloroacrylonitrile: inertial and principal quadrupole tensor components for Cl and N", J.Mol.Spectrosc., 184,215-220(1997).
  • CH2Cl2: Z.Kisiel, J.Kosarzewski, and L.Pszczolkowski, "Nuclear quadrupole coupling tensor of CH2Cl2: Comparison of quadrupolar and structural angles in methylene halides", Acta Physica Polonica A. 92, 507-516 (1997).Reprint
  • HCCl3: E.Bialkowska-Jaworska, Z.Kisiel and L.Pszczolkowski, "Nuclear quadrupole coupling in chloroform and calibration of ab initio calculations", J.Mol.Spectrosc., 238, 72-78 (2006).
  • CCl2=CH2:

    Z.Kisiel, E.Bialkowska-Jaworska, L.Pszczolkowski, "Nuclear quadrupole coupling in Cl2C=CHCl and Cl2C=CH2; Evidence for systematic differences in orientation between internuclear and field gradient axes for terminal quadrupolar nuclei", J.Chem.Phys. 109, 10263-10272 (1998).

    Z.Kisiel and L.Pszczolkowski, "The high-frequency rotational spectrum of 1,1-dichloroethylene", Z.Naturforsch. 50A, 347-351 (1995).

  • tBuX, X=F, Cl, Br, I, CN, NC: Z.Kisiel, E.Bialkowska-Jaworska, O.Desyatnyk, B.A.Pietrewicz, L.Pszczolkowski, "The gas-phase electric dipole moments of the symmetric top tertiary butyl molecules tBuX, X=F,Cl,Br,I,CN, and NC", J.Mol.Spectrosc., 208, 113-120 (2001).
  • 1-F-adamantane: A.C.Legon, J.Tizard, and Z.Kisiel, "Bridgehead distortion at the C1 position of 1-fluoroadamantane revealed by rotational spectroscopy and ab initio calculations", J.Mol.Struct., 612, 83-91 (2002).
  • Quinoline/Isoquinoline: Z.Kisiel, O.Desyatnyk, L.Pszczolkowski, C.B.Charnley, P.Ehrenfreund, "Rotational spectra of quinoline and of isoquinoline: spectroscopic constants and electric dipole moments", J.Mol.Spectrosc., 217, 115-122 (2003).
  • Camphor: Z.Kisiel, O.Desyatnyk, E.Bialkowska-Jaworska, L.Pszczolkowski, "The structure and electric dipole moment of camphor determined by rotational spectroscopy", Phys.Chem.Chem.Phys., 5, 1359-1364 (2003).
  • 1,3-benzodioxole: Z.Kisiel, L.Pszczolkowski, G.Pietraperzia, M.Becucci, W.Caminati, R.Meyer, "The anomeric effect in 1,3-benzodioxole: additional evidence from the rotational, vibration-rotation and rovibronic spectra", Phys.Chem.Chem.Phys., 6, 5469-5475 (2004).
  • Acetic acid/Acetone: O.Dorosh, Z.Kisiel, "Electric dipole moments of acetone and of acetic acid measured in supersonic expansion", Acta Physica Polonica A. 112, S95- S104  (2007).Reprint
  • Lactic acid:  L.Pszczolkowski, E.Bialkowska-Jaworska, Z.Kisiel, "The millimeter-wave rotational spectrum of lactic acid", J.Mol.Spectrosc., 234, 106-112 (2005).
  • Pyruvic acid: Z.Kisiel, L.Pszczolkowski, E.Bialkowska-Jaworska, S.B.Charnley, "The millimeter-wave rotational spectrum of pyruvic acid", J.Mol.Spectrosc., 241, 220-229 (2007).
 
     

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