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 FTIR Spectrum of the nu(12) Band of trans-d(2)-Ethylene

The nu(12) band of trans-d(2)-ethylene (trans-C(2)H(2)D(2)) has been recorded with an unapodized resolution of 0.0024 cm(-1) in the frequency range of 1240-1360 cm(-1) by Fourier transform infrared (FTIR) spectroscopy. This band was found to be relatively free from any local frequency perturbations. By fitting a total of 1185 infrared transitions of nu(12) with a standard deviation of 0.00043 cm(-1) using a Watson's A-reduced Hamiltonian in the I(r) representation, a set of accurate rovibrational constants for v(12) = 1 state was derived. The nu(12) band is A type with a band center at 1298.03797 +/- 0.00004 cm(-1). Copyright 2000 Academic Press.     

Analysis of the Coriolis Interaction between nu(6) and nu(8) Bands of HCOOH

The Fourier transform infrared (FTIR) spectrum of the nu(6) band of formic acid (HCOOH) has been recorded with a resolution of 0.0024 cm(-1) in the spectral range 1050-1160 cm(-1). The nu(6) band was found to be strongly perturbed by the nearby nu(8) band centered at about 1033.5 cm(-1). Using a Watson's A-reduced Hamiltonian in the I(r) representation, and with the inclusion of a-type Coriolis coupling constant, a simultaneous fit of nu(6) and nu(8) was performed. A total of 2485 infrared transitions including about 700 perturbed transitions of nu(6) and 19 transitions of nu(8) was fitted with an rms uncertainty of 0.0006 cm(-1). Accurate rovibrational constants up to sextic order for both nu(6) and nu(8) were obtained. The nu(6) band was analyzed to be a type AB hybrid with a band center at 1104.852109 +/- 0.000050 cm(-1). The band center for nu(8) was found to be 1033.4647 +/- 0.0021 cm(-1). Copyright 2000 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.     

The High-Resolution FTIR Spectrum of the nu(1) Band of DOBr

Fourier transform infrared spectra of the nu(1) bands of DO(79)Br and DO(81)Br have been recorded with a resolution of 0.0055 cm(-1) in the frequency range of 2510-2800 cm(-1). A total of 1901 lines of the A/B hybrid-type bands of both isotopic species have been assigned and fitted to upper state rovibrational constants employing a Watson's S-reduced Hamiltonian up to sextic terms. The K(a) >/= 4 subband transitions were found to be perturbed and were not included in the fit. The unperturbed band centers for nu(1) of DO(79)Br and DO(81)Br are 2668.79211 +/- 0.00006 and 2668.78842 +/- 0.00005 cm(-1), respectively. The ratio of the vibrational dipole transition moments (μ(a):μ(b)) was found to be 1.30 +/- 0.04 for the band. 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.     

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.     

Infrared intensity enhancement of the CN stretch of HCN by coadsorbed CO on the Cu(100) surface

Reflection absorption infrared spectra reveal a strong enhancement in the intensity of the CN stretch in a mixed ordered overlayer of HCN and CO on the Cu(100) surface. Various combinations of HCN and CO isotopomers show that the intensity enhancement decreases with increasing frequency difference between nu(CN) and nu(CO). The intensity of the 2092 cm(-1) band of H12C14N is enhanced by a factor of 155+/-20 through coupling to the 2077 cm(-1) band of 12C16O. A simple two-state coupling model explains the isotopomer dependence of the degree of enhancement.     

Rovibrational Study of the CH(2) Wagging Fundamental of Monofluoroacetonitrile

The vapor-phase infrared spectrum of monofluoroacetonitrile (CH(2)FCN) has been recorded at high resolution in the nu(4) band region (1363-1398 cm(-1)) using a tunable diode laser spectrometer. A detailed assignment of the rotational structure of the expected a-/b-hybrid band has been made for a-type transitions with K(a)相似文献   

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 and Millimeter-Wave Study of the Fermi-Coupled v(2) = 1 and v(3) = 2 States of DSiF(3)

The nu(2) (nu(eff.) 854.841 cm(-1)) and 2nu(3) infrared bands (nu(eff.) 840.083 cm(-1)) of DSiF(3) have been studied with a resolution of 2.5 x 10(-3) cm(-1). Moreover, millimeter-wave transitions in the v(2) = 1 and v(3) = 2 states up to J" = 33 have been measured. The assignments and fit of the poorly resolved, compressed cluster-type 2nu(3) IR transitions have been confirmed by a simultaneous study of the 2nu(3)-nu(3) band. The constant W = 5.116 cm(-1) of the Fermi interaction between the v(2) = 1 and v(3) = 2 levels has been determined from frequency effects which are in agreement with relative intensities of the nu(2) and 2nu(3) bands. The deperturbed (B(0) - B(v)) and (C(0) - C(v)) values of the states involved agree with their ab initio predictions within 7% in the worst case. Copyright 2001 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.     

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.     

Pulse Pyrolysis Infrared Laser Jet Spectroscopy of Chloroketene

The short-lived molecule chloroketene (ClHCCO) was generated by the pyrolysis of chloroacetyl chloride in a high-temperature nozzle and the infrared laser-absorption spectrum of its nu(2) fundamental band was measured between 2153 and 2161 cm(-1). The spectrum was greatly simplified by comparison with a room-temperature spectrum enabling 230 lines of the (35)ClHCCO isotopomer to be assigned and measured. A least-squares fit of these transitions yielded accurate molecular parameters for the v(2) = 1 state using ground state constants from microwave spectroscopy. The nu(2) band origin of (35)ClHCCO is 2157.19238(16) cm(-1). A comparison of simulated and experimental spectra showed that the rotational temperature of the jet spectrum was around 35 K. 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.     

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.     

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.     

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.