High-Resolution Absorption Spectroscopy of the 3nu(1) and 3nu(1) + nu(3) Bands of Propyne

The 3nu(1) and 3nu(1) + nu(3) bands of propyne have been recorded at Doppler-limited resolution by Fourier transform spectroscopy and intracavity laser absorption spectroscopy, respectively. The two bands show a mostly unperturbed J rotational structure for each individual K subband. However, as a rule the K structure ordering is perturbed in overtone transitions of propyne and different effective parameters associated with each K subband have been determined. From the vibrational energy levels, a value of -6.6 cm(-1) has been obtained for the x(13) cross anharmonicity in perfect agreement with the origins of the nu(1) + nu(3) and 2nu(1) + nu(3) combination bands estimated from the FTIR spectrum. Hot bands from the v(9) = 1 and v(10) = 1 levels associated with the 3nu(1) + nu(3) combination band have been partly rotationally analyzed and the retrieved values of x(39) and x(3,10) are in good agreement with literature values. Finally, the 4nu(1) + nu(9) - nu(9) band centered at 12 636.6 cm(-1) has been recorded by ICLAS. The red shift of this hot band relative to 4nu(1) and the DeltaB(v) value are discussed in relation to the anharmonic interaction between the 4nu(1) and 3nu(1) + nu(3) + nu(5) levels. 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.     

High-Resolution Laser Photoacoustic Spectroscopy of HSiF(3): The 5nu(1) and 6nu(1) Overtone Bands

A spectrum of HSiF(3) has been recorded at room temperature with a gas pressure of 20-50 Torr in the near-infrared region. A laser photoacoustic spectrometer consisting of a longitudinal resonant cell coupled to a titanium:sapphire ring laser was employed. The 5nu(1) and 6nu(1) overtone bands of H(28)SiF(3) associated with the Si-H stretching have been observed at high resolution (3 x 10(-2) cm(-1)) in the regions 10 900-10 960 and 12 875-12 925 cm(-1), respectively. About 450 lines of the 5nu(1)-0 band have been assigned (J 相似文献   

The nu(2) Band of Formaldehyde-d(2)

High-resolution Fourier transform infrared spectrum of the nu(2) band (1590-1780 cm(-1)) of deuterated formaldehyde D(2)CO has been recorded. More than 2500 rovibrational transitions have been assigned up to J(max) = 52 and K(max)(a) = 17. The upper state v(2) = 1 (A(1)) was found to be perturbed by a DeltaK(a) = 2 interaction with the v(4) = 2 (A(1)) state. To explain the resonance perturbation in the v(2) = 1 state, some lines of the 2nu(4) band (the band center at about 1868 cm(-1)) have also been assigned. Both bands were fitted simultaneously to the Watson-type rotational Hamiltonian using I(r) representation in A reduction, and the mutual interaction was taken into account. As a result, the rotational parameters of the v(2) = 1 state up to eighth order and the interaction parameter have been obtained. Copyright 2001 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.     

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 Spectrum and Rovibrational Analysis of the nu(2)/nu(5) Dyad of D(3)SiF near 700 cm(-1)

The nu(2) (A(1), 710.157 cm(-1)) and nu(5) (E, 701.717 cm(-1)) fundamental bands of D(3)(28)SiF have been studied by FTIR spectroscopy with a resolution of 2.4 x 10(-3) cm(-1). We assigned 1648 lines for the parallel band (J(max) = 50, K(max) = 21), 4279 for the perpendicular band (J(max) = 52, K(max) = 27), and in addition 671 perturbation-allowed transitions (J(max) = 50, K(max) = 12). The nearly degenerate v(2) = 1 and v(5) = 1 states are linked by (DeltaK = +/-1, Deltal = +/-1) and (DeltaK = +/-2, Deltal = -/+1) interactions, while the l(5) = +/-1 levels of nu(5) interact also by l(2, -1), l(2, 2), and l(2, -4) interactions. The first model with 36 free parameters, taking into account all these resonances through a nonlinear least-squares program, gave standard deviations of 1.56 x 10(-4) cm(-1) for 5997 nonzero-weighted IR data and 138 kHz for 8 MW data from the literature. The second model, in which the main Coriolis term was constrained to a force field value, used 37 parameters and gave similar standard deviations. A new determination of the A(0) and D(0)(K) ground state parameters was performed by two methods: either using differences between "forbidden" transitions differing by 3 in K or letting A(0) and D(0)(K) free in the global fit. The values obtained are fully compatible with those obtained previously by the "loop method." Copyright 2000 Academic Press.     

Rovibrational Analysis of the nu(2) Band of Diazirine-d(2)

The gas-phase IR spectrum of the nu(2) (A(1), 1610.33 cm(-1)) band of the deuterated isotopomer of diazirine, D(2)CN(2), a three-membered ring compound which belongs to the molecular symmetry point group C(2v), has been studied at a resolution of about 0.005 cm(-1). This vibrational mode which can be approximately described as N&dbond;N stretching is widely perturbed. This is due to various interactions with the tetrad consisting of the binary combinations nu(6) + nu(7) (A(1)), nu(7) + nu(9) (A(2)), nu(5) + nu(6) (B(2)), and nu(5) + nu(9) (B(1)), which form a relatively isolated pentad together with nu(2) in the wavenumber region 1560-1610 cm(-1). A simultaneous upper state analysis of nu(2) from a pentad model including these resonances has been performed and a set of spectroscopic parameters has been obtained. Since the four combination bands of the pentad are dark states, only band centers could be determined; in addition for nu(5) + nu(9) and nu(7) + nu(9) also the term (B - C)/2 has been obtained. A number of Coriolis interaction constants and the vibrational resonance (with nu(6) + nu(7)) parameter have been calculated as well. Copyright 2001 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.     

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.     

Torsional Splitting in the nu(5) Fundamental Infrared Band of CH(3)CD(3) and (13)CH(3)CD(3)

The nu(5) fundamental (C-C stretching) of CH(3)CD(3) shows a resolved torsional structure, caused by perturbations due mainly to the linear dependence of the torsional potential barrier on the normal coordinate Q(5). We were able to analyze this structure and to assign vibration-rotation transition wavenumbers for all five torsional components, classified according to the symmetry species of the G(18)((3)) extended molecular group. The torsional splitting pattern is qualitatively similar to that of a nondegenerate vibrational state with an even number of excited torsional quanta v(6). Explorative calculations show that the main perturber system should consist of the torsional components of the vibrational ground state correlating with v(6)=4 in the high barrier limit. The strength of the perturbation on the E(r0) torsional components of nu(5) increases rapidly with r, the E(40) component being the most affected. The observed transition wavenumbers can be reasonably fitted by a simplified model containing independent effective vibration-rotation parameters for the five different torsional components of nu(5), for both CH(3)CD(3) and (13)CH(3)CD(3). The trend of the determined values of the effective vibrational wavenumbers and rotational parameters over the torsional components supports the proposed vibration-torsion interaction mechanism, responsible for the observed torsional splittings. A strong anomaly observed in the rotational intensity distribution of nu(5) is discussed. Copyright 2001 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 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.     

New High-Resolution Analysis of the nu(3) Band of the (15)N(16)O(2) Isotopomer of Nitrogen Dioxide by Fourier Transform Spectroscopy

New high-resolution Fourier transform absorption spectra of an (15)N(16)O(2) isotopic sample of nitrogen dioxide were recorded at the University of Bremen in the 6.3-μm region. Starting from the results of a previous study [Y. Hamada, J. Mol. Struct. 242, 367-377 (1991)], a new and more extended analysis of the nu(3) band located at 1582.1039 cm(-1) has been performed. The spin-rotation energy levels were satisfactorily reproduced using a theoretical model which takes into account both the Coriolis interactions between the spin-rotation energy levels of the (001) vibrational state with those of the (020) and (100) states and the spin-rotation resonances within each of the NO(2) vibrational states. Precise vibrational energies and rotational, spin-rotation, and coupling constants were obtained in this way for the first triad of (15)N(16)O(2) interacting states {(020), (100), (001)}. Finally, a comprehensive list of line positions and line intensities of the {nu(1), 2nu(2), nu(3)} interacting bands of (15)N(16)O(2) was generated, using for the line intensities the transition moment operators which were obtained previously for the main isotopic species. 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.     

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.     

Theoretical Study of the Collision-Induced Double Transition CO(2) (nu(3) = 1) + N(2) (nu(1) = 1) <-- CO(2) (nu(3) = 0) + N(2) (nu(1) = 0) at 296 K

A procedure is presented for the calculation of the double vibrational collision-induced absorption CO(2) (nu(3) = 1) + N(2) (nu(1) = 1) <-- CO(2) (nu(3) = 0) + N(2) (nu(1) = 0) on the basis of quantum lineshapes computed using an isotropic potential and dipole-induced dipole functions. The linestrengths and energies of the vibration-rotation transitions are treated explicitly for N(2), utilizing the HITRAN database for CO(2). The theoretical absorption profile is compared to recent experimental results. By narrowing the width of the individual lines contributing to the overall absorption profile relative to their values determined for N(2)-N(2) collision-induced absorption, excellent agreement between theory and experiment is obtained. Copyright 2000 Academic Press.     

The 3nu(2) Band of D(2)(16)O

The 3nu(2) overtone band of deuterium oxide, D(2)O, centered at 3474.3193 cm(-1), has been measured with high resolution in a 4-m base-length White cell attached to a Fourier transform spectrometer. The analysis of the spectrum led to the assignment of 347 transitions in this band, defining rovibrational energy levels in the (030) state up to K(a) = 7 for J as high as 9, and lower K(a) levels for J as high as 16. The (030) state was treated as an isolated state, following a Padé-Borel approximation in the effective Hamiltonian. Of the 115 energy levels included in the analysis, 80% were reproduced by the 21 adjusted parameters to within 0.0008 cm(-1), and the largest error was 0.0017 cm(-1). 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.