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.     

The nu(12) Band of CH(3)SiD(3)

The lowest frequency degenerate fundamental band of CH(3)SiD(3) (v(12) = 1 <-- 0) centered around 418 cm(-1) was measured in order to investigate the vibration-torsion-rotation interactions in a symmetric-top molecule with a single torsional degree of freedom. The spectrum was recorded at an instrumental resolution of 0.004 cm(-1) using a Bomem Fourier transform spectrometer. The temperature and pressure of the sample were 180 K and 2 Torr, respectively. Because of the Coriolis coupling between the torsional stack with one quantum of the silyl rock excited and the corresponding stack for the ground vibrational state, torsional splittings are measured that are substantially larger than expected simply from the observed increase in the barrier height. Due to the local nature of the Coriolis perturbation, the significantly enhanced torsional splittings are confined to a few (K, varsigma) rotational series; here varsigma = -1, 0, 1 labels the torsional sublevels. The current measurements of the nu(12) band and frequencies from previously reported studies in the ground vibrational state were fitted to within experimental uncertainty using an effective Hamiltonian which was used for the analyses of similar spectra in CH(3)SiD(3) and CH(3)CD(3). Spectroscopic parameters characterizing the states v(12) = 0 and 1 and their interactions were determined, including several Coriolis-coupling constants. 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.     

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.     

Infrared and Millimeter-Wave Study of the Four Lowest Torsional States of CH(3)CF(3)

An investigation of the torsion-rotation Hamiltonian of CH(3)CF(3) in the ground vibrational state has been carried out using infrared and mm-wave spectroscopy. With infrared Fourier transform spectroscopy, the weak, torsional overtone (v(6) = 2 <-- 0) has been studied leading to the measurement of 382 frequencies between 405 and 440 cm(-1) at a resolution of 0.005 cm(-1). Torsional splittings on the order of 0.03 cm(-1) were observed. With mm-wave methods, a total of 669 rotational transitions between 50 and 360 GHz have been measured at Doppler-limited resolution in the four lowest torsional states v(6) = 0, 1, 2, 3. The experimental uncertainty attained for an isolated line was better than 10 kHz below 150 GHz, and somewhat larger at higher frequencies. For v(6) = 3, torsional splittings as large as 8.7 MHz were observed. The global data set consisted of the current frequency determinations and the 443 measurements with molecular beam, microwave, and mm-wave methods analyzed by I. Ozier, J. Schroderus, S.-X. Wang, G. A. McRae, M. C. L. Gerry, B. Vogelsanger, and A. Bauder [J. Mol. Spectrosc. 190, 324-340 (1998)]. The observation of mm-wave R-branch transitions for v(6) = 1 led to a change in the J-assignment of the forbidden (Deltak = +/-3) transitions reported earlier for this torsional state. A good fit was obtained by varying 24 parameters in a Hamiltonian that represented both the torsional effects and the sextic splittings. In the earlier work, the large reduced barrier height led to high correlations among several of the torsional distortion constants. With the current measurements, many of these correlations are substantially reduced. Improved effective values were determined for the height V(3) of the hindering barrier and the first-order correction V(6) in the Fourier expansion of the potential function. The dipole function which characterizes the transition moment of the torsional overtone (v(6) = 2 <-- 0) can be written as the product of a single effective dipole constant μ(T)(0,eff) and the appropriate off-diagonal matrix element of (1 - cos 3alpha)/2, where alpha is the torsional angle. From an intensity analysis of the infrared spectrum, it has been determined that |μ(T)(0,eff)| = 85.3(62) mD. A novel approach based on a simple regrouping of angular momentum operators is introduced for decoupling the torsional and rotational degrees of freedom. Copyright 2001 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.     

13C(16)O(2): Global Treatment of Vibrational-Rotational Spectra and First Observation of the 2nu(1) + 5nu(3) and nu(1) + 2nu(2) + 5nu(3) Absorption Bands

The effective operator approach is applied to the calculation of both line positions and line intensities of the (13)C(16)O(2) molecule. About 11 000 observed line positions of (13)C(16)O(2) selected from the literature have been used to derive 84 parameters of a reduced effective Hamiltonian globally describing all known vibrational-rotational energy levels in the ground electronic state. The standard deviation of the fit is 0.0015 cm(-1). The eigenfunctions of this effective Hamiltonian have then been used in fittings of parameters of an effective dipole-moment operator to more than 600 observed line intensities of the cold and hot bands covering the nu(2) and 3nu(2) regions. The standard deviations of the fits are 3.2 and 12.0% for these regions, respectively. The quality of the fittings and the extrapolation properties of the fitted parameters are discussed. A comparison of calculated line parameters with those provided by the HITRAN database is given. Finally, the first observations of the 2nu(1) + 5nu(3) and nu(1) + 2nu(2) + 5nu(3) absorption bands by means of photoacoustic spectroscopy (PAS) is presented. The deviations of predicted line positions from observed ones is found to be less than 0.1 cm(-1), and most of them lie within the experimental accuracy (0.007 cm(-1)) once the observed line positions are included in the global fit. Copyright 2000 Academic Press.     

First High-Resolution Infrared Observation of the Symmetry-Forbidden nu(5) Band of (10)B(2)H(6)

Spectra of (10)B monoisotopic diborane, B(2)H(6), have been recorded at high resolution (2-3 x 10(-3) cm(-1)) by means of Fourier transform spectroscopy in the region 700-1300 cm(-1). A thorough analysis of the nu(18) a-type, nu(14) c-type, and nu(5) symmetry-forbidden band has been performed. Of particular interest are the results concerning the nu(5) symmetry-forbidden band, which is observed only because it borrows intensity through an a-type Coriolis interaction with the very strong nu(18) infrared band located approximately 350 cm(-1) higher in wavenumber. The nu(5) band has been observed around 833 cm(-1) and consists of a well-resolved Q branch accompanied by weaker P- and R-branch lines. Very anomalous line intensities are seen, with the low K(a) transitions being vanishingly weak, and Raman-like selection rules observed. The determination of the upper state Hamiltonian constants proved to be difficult since the corresponding energy levels of each of the bands are strongly perturbed by nearby dark states. To account for these strong localized resonances, it was necessary to introduce the relevant interacting terms in the Hamiltonian. As a result the upper state energy levels were calculated satisfactorily, and precise vibrational energies and rotational and coupling constants were determined. In particular the following band centers were derived: nu(0) (nu(5)) = 832.8496(70) cm(-1), nu(0) (nu(14)) = 977.57843(70) cm(-1), and nu(0) (nu(18)) = 1178.6346(40) cm(-1). (Type A standard uncertainties (1varsigma) are given in parentheses.) Copyright 2000 Academic Press.     

High-Resolution Infrared Spectrum of CD(3)CN: Analysis of the Interacting nu(3) and nu(6) Bands and Evaluation of the A(0) Constant

The infrared spectrum in the range 900-1230 cm(-1) including the fundamental bands nu(3) and nu(6) of CD(3)CN has been studied. The resolution attained was 0.0025 cm(-1) in the measurement on the Bruker 120 HR Fourier spectrometer in Oulu. About 4000 lines were assigned in the nu(6) band. For the weak nu(3) band, which has not been observed earlier directly, we were able to assign 206 lines in three subbands K=8-10. These lines become detectable due to the strong nu(3)/nu(6) Coriolis resonance. There is also an l(1,-2) resonance between nu(3) and nu(6), which made it possible to obtain a value 2.647721(50) cm(-1) for the axial rotational constant A(0), when D(0)(K) from force field calculations was applied. Different types of resonances with the overtone 3nu(8) and the combinations nu(4)+nu(8) and nu(7)+nu(8) were observed. A fit with a standard deviation of 0.0019 cm(-1) was attained by using a model of 10 different resonances. Copyright 2001 Academic Press.     

Torsional Splitting in the Degenerate Vibrational States of (70)Ge(2)H(6): Rotation-Torsion Analysis of the nu(7) and nu(9) Fundamentals

The rotational and torsional structure of the nu(7) and nu(9) degenerate fundamentals of (70)Ge(2)H(6) has been analyzed under high resolution. The torsional structure of both v(7) = 1 and v(9) = 1 states can be fitted by a simple one-parameter formula. The x,y-Coriolis interaction with the parallel nu(5) fundamental was accounted for in the analysis of nu(7). A strong perturbation of the J structure of the E(3s) torsional component of the KDeltaK = -2 subbranches of nu(9) can be explained by the resonance with an E(3s) excited level of the pure torsional manifold. The perturber is centered at 361.58 cm(-1), very close to the value estimated with a barrier height of 285 cm(-1). This confirms that the fundamental torsional wavenumber is close to 103 cm(-1), in good agreement with the "ab initio" prediction. The torsional splittings of all the infrared active degenerate fundamentals, nu(7), nu(8), and nu(9), follow the trend predicted by theory, and have been fitted by exploratory calculations accounting only for the torsional Coriolis-coupling mechanism of all degenerate vibrational fundamentals in several torsional states. This confirms that torsional Coriolis coupling is the dominant mechanism responsible for the decrease of the torsional splitting in the degenerate vibrational states. A higher value of the barrier had to be used for the nu(9) mode. Copyright 2000 Academic Press.     

High-Resolution Analysis of the nu(4) Absorption Band of CH(2)(79)BrF

The gas-phase infrared spectrum of the nu(4) fundamental band of CH(2)(79)BrF was recorded in the 1010-1116 cm(-1) wavenumber region using a TDL spectrometer. In this first high-resolution investigation of the synthesized (79)Br isotopic form, more than 10 200 transitions of this a/b-hybrid band centered at 1068.5385 cm(-1) were assigned and, using the Watson's A-reduced Hamiltonian in the I(r)-representation, a reliable set of molecular constants for the excited state v(4) = 1 was determined. From ground state combination differences having rotational quantum numbers J and K(a) up to 97 and 21, respectively, improved and extended ground state rotational and centrifugal distortion constants were calculated as well. Comparison between the observed and calculated band intensities in appropriate regions of the spectrum gave an estimate of the transition dipole-moment ratio along the a and b axes as ||Deltaμ(a)/Deltaμ(b) || = 2.0 +/- 0.2, in agreement with the predicted theoretical value of 1.99. Copyright 2000 Academic Press.     

High-Resolution Infrared Spectrum of BrCN in the nu(2) and nu(1)/2nu(2) Regions

The vibrational excitations of bent triatomic molecules, including both bending and stretching vibrations, are studied in the framework of the U(4) algebra. For the bent triatomic molecules H(2)O and H(2)S, the highly excited vibrational levels (up to 14) are obtained using the U(4) algebraic approach. We have found that the spectra are made up of clustering structure. The number of levels in one cluster depends on the total quanta of stretching and bending. In addition, some other properties are also discussed. Copyright 2000 Academic Press.     

H(2)-Broadening Coefficients in the nu(4) Band of NH(3)

H(2)-broadening coefficients have been measured for 66 rovibrational lines of NH(3) at room temperature in the (P)P and (R)P branches of the nu(4) band in the range 1470-1600 cm(-1), using a high-resolution Fourier transform spectrometer. The collisional widths are obtained by fitting Voigt profiles to the measured shapes of the lines. The broadening coefficients are found to decrease on the whole as J increases and they increase with K for a given J value. The results are compared with those calculated from a semiclassical model in which the inversion vibration of NH(3) and collision-induced transitions with DeltaK = 0 and DeltaK = +/- 3 are taken into account. The intermolecular potential used includes electrostatic, induction, and dispersion energy contributions. The calculations performed by considering only DeltaK = 0 transitions provide significantly lower broadenings but with a satisfactory J and K dependence. The same trends are obtained for the broadening coefficients in inversion-rotation transitions and in the Q branch of the nu(1) parallel band of NH(3). Copyright 2001 Academic Press.     

Sub-Doppler Infrared Spectra of the OH-Stretch Fundamental of (13)C-Methanol

High-resolution infrared spectra of the (13)C-methanol OH stretching band, nu(1), were obtained by slit-jet absorption spectroscopy at a rotational temperature of 12-15 K. Twenty-eight subbands were assigned within the range of upper state quantum numbers, K' = 0 to 2 and J' = 0 to 10. The upper state energy levels are heavily perturbed; about half of the assigned subbands were found to be split by perturbations with matrix elements in the range 1-3 cm(-1). The doubled lines were deperturbed and together with the "unperturbed" lines were fitted to a global torsion-rotation Hamiltonian with root-mean-square deviation of 0.41 cm(-1) to yield a torsional barrier height of approximately 405 cm(-1) in the vibrationally excited state. Copyright 2000 Academic Press.     

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.     

Analysis of the nu(12) Band of Ethylene-(13)C(2) by High-Resolution FTIR Spectroscopy

The Fourier transform infrared (FTIR) spectrum of the nu(12) fundamental band of ethylene-(13)C(2) ((13)C(2)H(4)) was recorded with an unapodized resolution of 0.004 cm(-1) in the frequency range from 1380 to 1500 cm(-1). Rovibrational constants for the upper state (nu(12)=1) up to five quartic and three sextic centrifugal distortion terms were derived for the first time by assigning and fitting a total of 1177 infrared transitions using a Watson's A-reduced Hamiltonian in the I(r) representation. The rms deviation of the fit was 0.00045 cm(-1). The ground state rovibrational constants were also determined for the first time by a fit of 738 combination differences from the present infrared measurements, with a rms deviation of 0.00060 cm(-1). The A-type nu(12) band with a band center at 1436.65411+/-0.00005 cm(-1) was found to be relatively free from local frequency perturbations. The inertial defect Delta(12) was found to be 0.24300+/-0.00002 u?(2). Copyright 2001 Academic Press.     

High-Resolution Infrared Spectrum of the Ring-Puckering Band, nu(10), of Diborane

The spectrum of the nu(10) band of diborane, arising from the ring-puckering vibration, has been obtained with a spectral resolution of 0.0015 cm(-1) in the region 275-400 cm(-1). The spectrum of a sample enriched in (10)B was recorded as well as one with naturally abundant boron, i.e., 64% (11)B(2)H(6), 32% (10)B(11)BH(6), and 4% (10)B(2)H(6). This mode is the lowest vibrational level of the molecule and is unperturbed, allowing a complete assignment of not only the fundamental bands but also the 2nu(10)-nu(10) hot bands of all three boron isotopomers. The intensities of several hundred lines of the fundamental and hot bands of all isotopomers have been measured and vibrational transition moments have been obtained. Finally, it has been shown that the harmonic approximation does not apply for nu(10). Copyright 2000 Academic Press.     

Spectroscopy and Intensity Measurements of the 3nu(1)+3nu(3) Tetrad of (12)CO(2) and (13)CO(2)

Three of the four components of the 3nu(1)+3nu(3) tetrad of (12)C(16)O(2) and (13)C(16)O(2), labeled 30031, 30032, and 30033 in HITRAN notation, have been observed by intracavity laser absorption spectroscopy in the 10 450- to 11 000-cm(-1) region. The rotational analysis has yielded the rovibrational parameters of the vibrational states. The experimental values are found to be in very good agreement with the rovibrational energies recently predicted from variational calculations and reduced effective Hamiltonians. The absolute band intensity of these extremely weak transitions have been measured. The study of the relative intensities within the 3nu(1)+3nu(3) tetrad suggests that part of the oscillator strength is carried by the (22(0)3) state. Copyright 2001 Academic Press.