High-Resolution Infrared, Microwave, and Submillimeter-Wave Study of FClO(2) in the nu(2), nu(3), nu(4), and nu(6) Excited States

A high-resolution analysis of the {nu(2), nu(3)} and {nu(4), nu(6)} bands of the two isotopomers of chloryl fluoride F(35)ClO(2) and F(37)ClO(2) has been carried out for the first time using simultaneously infrared spectra recorded around 16&mgr;m and 26&mgr;m with a resolution of ca. 0.003 cm(-1) and microwave and submillimeter-wave transitions occurring within the vibrational states 2(1), 3(1), 4(1), and 6(1). Taking into account the Coriolis resonances which link the rotational levels of the {2(1), 3(1)} and the {4(1), 6(1)} interacting states, it was possible to reproduce very satisfactorily the observed transitions and to determine accurate vibrational energies and rotational constants for the upper states 2(1), 3(1), 4(1), and 6(1) of both the (35)Cl and (37)Cl isotopic species. Copyright 2001 Academic Press.     

High Resolution FTIR Spectroscopy of DCCCl: Anharmonic Resonances in the nu(1) and nu(2) Bands

High-resolution infrared spectra of the nu(1) and nu(2) bands of DCCCl were observed using Bruker IFS 120HR Fourier transform spectrometers at resolutions of 0.0044 and 0.0035 cm(-1), respectively. For the DCC(35)Cl isotopomer, the nu(1) as well as the nu(2) band was found to be heavily perturbed. Detailed analyses revealed that the nu(1) state is in resonance with the l=0 substate of the nu(3)+4nu(4) state and that the nu(2) state is in resonance with the l=0 substate of the nu(3)+4nu(5) state. The rotational constants played a key role in identifying the perturbing states. In contrast, for the DCC(37)Cl isotopomer, the rotational structures of the nu(1) and nu(2) states are almost regular but slightly perturbed by interactions with the nu(3)+4nu(4) and nu(3)+4nu(5) states, respectively. The constants of resonances as well as the molecular constants for the nu(1), nu(2), nu(3)+4nu(4) and nu(3)+4nu(5) states were determined. Copyright 2001 Academic Press.     

Infrared Diode Laser Spectrum of the nu(1) Fundamental Band of ClBO

The nu(1) band of ClBO has been recorded using infrared diode laser spectroscopy. The molecule was produced by reacting oxygen atoms, produced in a microwave discharge containing an O(2)/He mixture, with BCl(3). Thirty-three lines of the (35)Cl(11)B(16)O isotopomer and 32 lines due to the (37)Cl(11)B(16)O isotopomer have been assigned. By fixing the ground state constants to those previously obtained by microwave spectroscopy, a least-squares fit (rms = 0.0008) gave the following upper state constants; (35)Cl(11)B(16)O: nu(0) = 1972.18024(21) cm(-1), B(1) = 0.1725055(12) cm(-1); (37)Cl(11)B(16)O: nu(0) = 1971.82846(24) cm(-1), B(1) = 0.1688402(13) cm(-1). The rotational constants of all the fundamental bands of ClBO have been used to calculate an r(e) structure yielding r(e(B-Cl)) = 167.668(26) pm and r(e(B-O)) = 121.308(26) pm. Copyright 2000 Academic Press.     

Diode-Laser Spectroscopy of the nu(19a) Band of Chlorobenzene in a Supersonic Jet

The diode-laser absorption spectrum of the nu(19a) band of the chlorobenzene molecule cooled in a supersonic jet is presented and transitions from low J, K(a), and K(c) values (0-14) are reported. The C(6)H(5)(35)Cl band center has been found at nu(0) = 1483.894 cm(-1) and rotational constants for the upper state have been determined from a least-squares fitting to experimental data. The band center for the C(6)H(5)(37)Cl isotope has also been obtained. Copyright 2000 Academic Press.     

Fourier Transform Infrared Spectra of CH(2)DF: The nu(5) and nu(6) Bands

Results of a high-resolution infrared study of the spectroscopy of monodeuterated methyl fluoride, CH(2)DF, are reported for the first time. Spectra ranging from 500 to 3300 cm(-1) have been obtained and cover all the fundamental bands at resolutions down to 0.005 cm(-1). The two lowest energy fundamentals, the nu(5) and nu(6) bands, have been analyzed in detail. Since the molecule has C(s) symmetry, in principle both these bands are AB hybrids, since they belong to the irreducible representation A'. However, it was found that both are almost pure A-type bands. A total of 597 A-type lines of the nu(5) band and 619 A-type lines of the nu(6) band have been assigned. Vibrational and rotational spectroscopic constants have been determined by least-squares fitting to the data. An improved band center for nu(7) is also reported. Copyright 2001 Academic Press.     

High-Resolution Infrared Study of the nu(7), nu(8), and nu(15) Bands and Millimeter-Wave Investigation of the v(8) = 1 State of CF(2)Cl-CH(3)

High-resolution (Deltavarsigma = 2.3 and 2.9 x 10(-3) cm(-1)) FTIR spectra of natural and (35)Cl monoisotopic CH(3)CF(2)Cl have been recorded at -70 degrees C in the 600-1400 cm(-1) range. The bands nu(7), nu(8), and nu(15) have been rotationally analyzed for both isotopic varieties. With the help of predictions based on nu(8) parameters, the millimeter-wave spectrum of the (35)Cl species in the v(8) = 1 state has been observed and jointly fitted with the IR data. Only a small number of local perturbations have been detected in the spectra. Altogether more than 8000 IR transitions have been fitted with an experimental precision of ca. 3 x 10(-4) cm(-1). Copyright 2000 Academic Press.     

The nu(1) and nu(3) Bands of the (17)O(16)O(17)O Isotopomer of Ozone

Using 0.002 cm(-1) resolution Fourier transform absorption spectra of an (17)O-enriched ozone sample, an extensive analysis of the nu(3) band together with a partial identification of the nu(1) band of the (17)O(16)O(17)O isotopomer of ozone has been performed for the first time. As for other C(2v)-type ozone isotopomers [J.-M. Flaud and R. Bacis, Spectrochim. Acta, Part A 54, 3-16 (1998)], the (001) rotational levels are involved in a Coriolis-type resonance with the levels of the (100) vibrational state. The experimental rotational levels of the (001) and (100) vibrational states have been satisfactorily reproduced using a Hamiltonian matrix which takes into account the observed rovibrational resonances. In this way precise vibrational energies and rotational and coupling constants were deduced and the following band centers nu(0)(nu(3)) = 1030.0946 cm(-1) and nu(0)(nu(1)) = 1086.7490 cm(-1) were obtained for the nu(3) and nu(1) bands, respectively. Copyright 2000 Academic Press.     

Microwave, Submillimeter-Wave, and High-Resolution FTIR Study of SO(2)F(2) in the nu(8) State

The high-resolution infrared spectrum of the nu(8) band of SO(2)F(2) (nu(as) SF(2)) centered at 887.2 cm(-1) has been recorded with a resolution of 2.4 x 10(-3) cm(-1). More than 8000 transitions of the C-type band with DeltaK(a) = +/-1 (and in addition some DeltaK(a) = +/-3 transitions) have been assigned. Microwave and millimeter-wave spectra of the v(8) = 1 state up to 450 GHz have been recorded, and 177 pure rotational transitions have been measured. Rotational and rovibrational data have been combined, and excited state parameters up to sextic centrifugal distortion constants have been determined using a Watson-type Hamiltonian in S-reduction. No perturbation was indicated. Copyright 2000 Academic Press.     

The High-Resolution FTIR Spectrum and Equilibrium Structure of Chloro(sulphido)boron

The FTIR spectrum of chloro(sulphido)boron, Cl-B&bond;S, has been recorded at 0.0035 cm(-1) resolution. The nu(3) bands of the isotopomers (35)Cl(11)B(32)S, (37)Cl(11)B(32)S, (35)Cl(11)B(34)S, (37)Cl(11)B(34)S, (35)Cl(10)B(32)S, (37)Cl(10)B(32)S, and (35)Cl(10)B(34)S have been analyzed to yield effective rotational and centrifugal distortion constants for the ground and a number of excited vibrational states. For the (35)Cl(11)B(32)S isotopomer the nu(1) band has also been analyzed. The rotational constants have been used to determine equilibrium bond lengths of 168.42(8) and 160.14(8) pm for the Cl-B and B-S bonds, respectively. Copyright 2000 Academic Press.     

New High-Resolution Analysis of the 3nu(3) and 2nu(1) + nu(3) Bands of Nitrogen Dioxide (NO(2)) by Fourier Transform Spectroscopy

Using new high-resolution Fourier transform spectra recorded at the University of Denver in the 2-μm region, a new and more extended analysis of the 2nu(1) + nu(3) and 3nu(3) bands of nitrogen dioxide, located at 4179.9374 and 4754.2039 cm(-1), respectively, has been performed. The spin-rotation energy levels were satisfactorily reproduced using a theoretical model that takes into account both the Coriolis interactions between the spin-rotation energy levels of the (201) vibrational "bright" state with those of the (220) "dark" state. The interactions between the (003) bright state with the (022) dark state were similarly treated. The spin-rotation resonances within each of the NO(2) vibrational states were also taken into account. The precise vibrational energies and the rotational, spin-rotational, and coupling constants were obtained for the two dyads {(220), (201)} and {(022), (003)} of the (14)N(16)O(2) interacting states. From the experimental line intensities of the 2nu(1) + nu(3) and 3nu(3) bands, a determination of their vibrational transition moment constants was performed. A comprehensive list of line positions and line intensities of the {2nu(1) + 2nu(2), 2nu(1) + nu(3)} and the {2nu(2) + 2nu(3), 3nu(3)} interacting bands of (14)N(16)O(2) was generated. In addition, assuming the harmonic approximation and using the Hamiltonian constants derived in this work and in previous studies (A. Perrin, J.-M. Flaud, A. Goldman, C. Camy-Peyret, W. J. Lafferty, Ph. Arcas, and C. P. Rinsland, J. Quant. Spectrosc. Radiat. Transfer 60, 839-850 (1998)), we have generated synthetic spectra for the {(022), (003)}-{(040), (021), (002)} hot bands at 6.3 μm and for the {(220), (201)}-{(100), (020), (001)} hot bands at 3.5 μm, which are in good agreement with the observed spectra. Copyright 2000 Academic Press.     

Millimeter-Wave Spectroscopy of Sulfur Dichloride

The rotational spectra of (32)S(35)Cl(2), (32)S(35)Cl(37)Cl, (32)S(37)Cl(2), and (34)S(35)Cl(2) in their ground vibrational states, as well as those of (32)S(35)Cl(2) and (32)S(35)Cl(37)Cl in their nu(2) and 2nu(2) excited states, have been studied in selected frequency regions between 100 and 370 GHz. Transitions involving a large range of quantum numbers have been observed, so that precise rotational and quartic centrifugal distortion constants could be determined for each of the spectra investigated. The complete set of sextic distortion constants was also obtained for the most abundant isotopomer in its ground vibrational state. The newly determined rotational constants of (34)S(35)Cl(2) and (32)S(37)Cl(2) allowed us to calculate the complete r(s) structure of sulfur dichloride using both single- and double-isotopic substitution methods. The quadratic force field has been refined using a larger set of quartic distortion constants and inertial defects. Copyright 2000 Academic Press.     

Simultaneous Analysis of the nu(2) Raman and nu(2) + nu(6) Infrared Spectra of the SF(6) Molecule

High-resolution Raman spectra of the nu(2) band of SF(6) have been recorded at a temperature of 195 K (dry ice) and a pressure of 39 mbar. These spectra were analyzed using a new set of programs specially written for XY(6) molecules. These programs, called HTDS (highly spherical top data system) in reference to the set of programs called STDS (spherical top data system written for XY(4) molecules) can be freely accessible through ftp (user anonymous) at jupiter.u-bourgogne.fr or on the web at the URL http://www.u-bourgogne.fr/LPUB/shTDS.html. The study of nu(2) was made using a Hamiltonian developed through the third order. Four parameters were determined. The standard deviation obtained using about 559 data up to J < 61 is 0.0021 cm(-1). This result is used to refine by simultaneous analysis the nu(2) and nu(2) + nu(6) bands of SF(6). This new fit allows the determination for the first time of some nu(6) parameters. The values obtained for this band (forbidden in Raman and in infrared) will be used to study the infrared hot bands in the nu(3) and nu(4) regions. Copyright 2000 Academic Press.     

The nu(2), nu(4) + nu(5), nu(6) + nu(9), and nu(8) Band System in 1,1,1-Trifluoroethane

High-resolution FTIR spectra of 1,1,1-trifluoroethane (HFC-143a) have been recorded in the region from 1370 to 1470 cm(-1) with an unapodized resolution of 0.0016 cm(-1) at room temperature and of 0.004 cm(-1) at 183 and 100 K. The two main infrared active bands of A(1) symmetry have been shown to be nu(2) at 1407.5 cm(-1) and nu(4) + nu(5) at 1440.5 cm(-1). With the aid of Raman spectra, the two infrared inactive bands of E symmetry in this spectra region have been shown to be nu(8) at 1457.5 cm(-1) and nu(6) + nu(9) at 1446.2 cm(-1). The nu(2) band was analyzed as an isolated band, whereas the nu(4) + nu(5) band was analyzed as part of the triad nu(4) + nu(5), nu(6) + nu(9), and nu(8). Copyright 2000 Academic Press.     

The Coriolis Interaction between the nu(9) and nu(7) Fundamental Bands of Methylene Fluoride

The infrared spectrum of the nu(12) fundamental band of ethylene (C(2)H(4)) has been measured with an unapodized resolution of 0.004 cm(-1) in the frequency range of 1380-1500 cm(-1) using the Fourier transform technique. By assigning and fitting a total of 1387 infrared transitions using a Watson's A-reduced Hamiltonian in the I(r) representation, rovibrational constants for the upper state (v(12) = 1) up to five quartic and three sextic centrifugal distortions terms were derived. They represent the most accurate constants for the band so far. The rms deviation of the fit was 0.00033 cm(-1). The A-type nu(12) band with a band center at 1442.44299 +/- 0.00003 cm(-1) was found to be relatively free from local frequency perturbations. The inertial defect Delta(12) was found to be 0.24201 +/- 0.00002 u ?(2). Copyright 2000 Academic Press.     

High-Resolution FTIR Spectrum of the nu(9) Band of Ethylene-D(4) (C(2)D(4))

The spectrum of the nu(9) fundamental band of ethylene-d(4) (C(2)D(4)) has been measured with an unapodized resolution of 0.004 cm(-1) in the frequency range of 2300-2400 cm(-1) using a Fourier transform infrared spectrometer. A total of 549 transitions have been assigned and fitted using a Watson's A-reduced Hamiltonian in the I(r) representation to derive rovibrational constants for the upper state (v(9) = 1) up to five quartic terms with a standard deviation of 0.00087 cm(-1). They represent the most accurate rovibrational constants for the nu(9) band so far. About 30 transitions of K(a)(') = 0, one transition of nu(9) which were identified to be perturbed possibly by the nearby nu(11) and nu(2) + nu(12) transitions, were not included in the final fit. The nu(9) band of C(2)D(4) was found to be basically B-type with an unperturbed band center at 2341.836 94 +/- 0.000 13 cm(-1). Copyright 2000 Academic Press.     

High-Resolution Fourier Transform and Diode-Laser Spectroscopy of the nu(6) Fundamental of C(2)F(6) and Associated Hot Bands

High-resolution infrared spectra of the nu(6) (713 cm(-1)) band region of C(2)F(6) vapor have been recorded at several temperatures. Spectra at 77, 200, and 300 K were recorded using a Fourier transform spectrometer with unapodized resolutions of 0.0018 cm(-1) (200 and 300 K) and 0.008 cm(-1) (77 K). Spectra with rotational temperatures in the range 5-50 K were recorded in a supersonic jet using diode-laser absorption spectroscopy. The nu(6) band contains two clear sequences of hot-bands: one arises from the nu(4) torsional vibration at 67.5 cm(-1); the other, shorter, weaker progression is built on the doubly degenerate nu(9) vibration at 220 cm(-1). They lie to high and low wavenumbers of the fundamental band, respectively. Eleven series were assigned and fitted to these hot bands. A perturbed series in the nu(4) sequence is considered, by analogy with the infrared spectrum of C(2)H(6) vapor, to be caused by an xy-Coriolis interaction either between 5nu(4) and nu(9) + 2nu(4) in the ground state or, in the upper state, nu(6) + 5nu(4) with nu(6) + nu(9) + 2nu(4) or nu(6) + 5nu(4) with 2nu(8). One further series resolved only in the jet spectrum and lying very close to the fundamental is almost certainly due to the nu(6) fundamental of the isotopomer (13)C(12)CF(6). Copyright 2000 Academic Press.     

Rotational Analysis of the Ground State and the Lowest Fundamentals nu(3), nu(5), and nu(6) of (13)CH(3)D

The nu(3), nu(5), and nu(6) fundamental bands of the (13)CH(3)D molecule have been studied with Fourier transform infrared spectroscopy. The spectra and results for the parent species (12)CH(3)D (O. N. Ulenikov, G. A. Onopenko, N. E. Tyabaeva, J. Schroderus, and S. Alanko, J. Mol. Spectrosc. 193, 249-259 (1999)) have been used to assign and analyze about 1900 lines belonging to the (13)CH(3)D isotopic species. About 850 ground state combination differences with DeltaK = 0 were calculated, which allowed us to determine the J-dependent ground state rotational constants. The K-dependent constants as well as those describing the a(1)-a(2) (K = 3) splitting were fixed to the values obtained for the (12)CH(3)D species. The (v(3) = 1), (v(5) = 1), and (v(6) = 1) states were fit simultaneously by including the intervibrational interactions in the Hamiltonian. The rotational energies, the rotational and centrifugal distortion constants, as well as the resonance parameters involving the three states have been determined and discussed. Copyright 2000 Academic Press.     

Absolute Line Intensities and Self-Broadening Coefficients in the nu(1) Band of (35)Cl(12)C(14)N

The self-broadening coefficients and the intensities of 29 lines in the nu(1) band of cyanogen chloride ((35)Cl(12)C(14)N) have been measured at high resolution in the range 699-736 cm(-1), using a tunable diode-laser spectrometer. The collisional widths and most of the intensities are obtained by fitting Voigt and Rautian profiles to the measured shapes of the lines. From the analysis of the line intensities we determine the absolute strength as well as the Herman-Wallis factors for the nu(1) band. A semiclassical calculation of the self-broadening coefficients, performed by considering the main electrostatic interactions only, has provided larger results than the experimental data. Copyright 2001 Academic Press.     

Absolute nu(2) Line Intensities of HOCl by Simultaneous Measurements in the Infrared with a Tunable Diode Laser and Far-Infrared Region Using a Fourier Transform Spectrometer

We have measured absolute line intensities in the nu(2) fundamental band at 1238 cm(-1) of both isotopomers of hypochlorous acid, HOCl. To obtain the partial pressure of the species in the sample mixture, unavailable through direct measurement since HOCl exists only in equilibrium with H(2)O and Cl(2)O and may decay by secondary reactions, we relied on known absolute line intensities in the pure rotational far-infrared (FIR) spectrum determined from Stark effect measurements. We have thus recorded simultaneously the FIR pure rotation spectrum of HOCl using a Bruker IFS120HR interferometer and the spectrum of a few vibration-rotation lines in the infrared (IR) nu(2) band using a tunable diode laser spectrometer. The absolute intensities of these IR lines thus determined allowed us to "calibrate" the intensities of vibration-rotation lines in the whole nu(2) band, measured previously using Fourier transform spectroscopy. The treatment of the data took into account the blackbody emission contribution in the FIR and the evolution of the HOCl amount during the recording of the spectra. The latter was found to be almost constant over hours after conditioning of the cell. The square of the nu(2) band vibrational transition dipole moment was determined to be 0.013947(23) D(2) and 0.013870(51) D(2) for HO(35)Cl and HO(37)Cl, respectively, that is, 29 to 73% lower than previous measurements. A linear Herman-Wallis factor was also determined for both isotopomers. Finally, the line intensities were least-squares fitted using a model that takes into account a weak resonance between the (010) and (002) levels. Copyright 2000 Academic Press.     

High-Resolution Infrared Spectra in the C-H Region of CH2F2: The nu6 and 2nu2 Bands

High-resolution, infrared absorption spectra of the nu6 (asymmetric C-H stretch) and 2nu2 (H-C-H symmetric bend overtone) bands of jet-cooled CH2F2 are reported with a sub-Doppler resolution of approximately 0.002 cm-1. More than 600 transitions were observed in the range of 3002-3036 cm-1, of which 268 were assigned the nu6 fundamental and 184 were assigned to the 2nu2 overtone. A fit of the nu6 band to the A-reduced Watson Hamiltonian yielded eight effective constants including nu0 = 3014.0503(1), A' = 1.62868(4), B' = 0.354165(5), and C' = 0.308852(3) cm-1. Similarly, the weaker 2nu2 band was fit to seven parameters including nu0 = 3026.2297(2), and A' = 1.63396(6), B' = 0.35367(1), and C' = 0.31183(1) cm-1. Numbers in parentheses are two standard deviations in units of the last digit. Anomalous values of the A rotational constant and the DeltaK centrifugal distortion constant are attributed to an a-axis Coriolis interaction between the 2nu2 and nu6 bands. The relative intensity of the 2nu2 band is used to estimate the stretch-bend anharmonic interaction with nu1. Copyright 1999 Academic Press.