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.     

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.     

Absolute Intensities of the 10-µm Bands of (16)O(3)

Two hundred ninety experimental absolute intensities of nu(1) and nu(3) transitions of ozone have been measured, with good accuracy (<2%). They are used to derive the transition-moment parameters for these bands. The agreement between our observed and calculated line intensities is satisfactory. This work shows that the intensities of these two bands are on average 4% smaller than those used in the literature. In addition, 20 intensities of the nu(2) + nu(3) - nu(2) band confirm this value. Also, 42 line intensities of the 2nu(1)-nu(3) band are reported. Copyright 2001 Academic Press.     

Absolute Line Intensities for the nu6 Band of H2O2

The purpose of this work was to obtain reliable absolute intensities for the nu6 band of H2O2. It was undertaken because strong discrepancies exist between the different nu6 band intensities which are presently available in the literature (A. Perrin, A. Valentin, J.-M. Flaud, C. Camy-Peyret, L. Schriver, A. Schriver, and P. Arcas, J. Mol. Spectrosc. 1995. 171, 358), (R. May, J. Quant. Radiat. Transfer 1991. 45, 267), and (R. L. Sams, personal communication). The method which was chosen in the present work was to measure simultaneously the far-infrared absorptions and the nu6 absorptions of H2O2. Consequently, Fourier transform spectra of H2O2 were recorded at Giessen in a spectral range (370-1270 cm-1) which covers both the R branch of the torsion-rotation band and the P branch of the nu6 band which appear at low and high wavenumbers, respectively. From the low wavenumber data, the partial pressure of H2O2 present in the cell during the recording of the spectra was determined by calibrating the observed absorptions in the torsion-rotation band with intensities computed using the permanent H2O2 dipole moment measured by Stark effect (A. Perrin, J.-M. Flaud, C. Camy-Peyret, R. Schermaul, M. Winnewisser, J.-Y. Mandin, V. Dana, M. Badaoui, and J. Koput, J. Mol. Spectrosc. 1996. 176, 287-296) and [E. A. Cohen and H. M. Pickett, J. Mol. Spectrosc. 1981. 87, 582-583). In the high frequency range, this value of the partial pressure of H2O2 was used to measure absolute line intensities in the nu6 band. Finally, the line intensities in the nu6 band were fitted using the theoretical methods described in detail in our previous works. Using these new results on line intensities together with the line position parameters that we obtained previously, a new synthetic spectra of the nu6 band was generated, leading to a total band intensity of 0.185 x 10(-16) cm-1/(molecule.cm-2) at 296 K. It has to be pointed out that the new line intensities agree to within the experimental uncertainties with the individual line intensity measurements performed previously by May and by Sams. Copyright 1999 Academic Press.     

Line intensities of the ν3 fundamental band of nitrous oxide

The line strengths are measured for 30 vibration-rotation lines of the nitrous oxide fundamental band ν₃. The intensity distribution as a function of J is analyzed. The band strength and the vibration-rotation interaction effect on line intensities are deduced.     

Infrared and far-infrared laser emissions from a TE CO2 laser pumped NH3 gas

In this paper, infrared (IR) and far-infrared (FIR) laser emissions from a TE CO₂ laser pumped NH₃ gas are reported. 8 IR laser emissions near the wavelength of 12 μm were observed by using 4 different CO₂ laser lines for the pumping. 3 IR laser emissions in P-branch of vibrational-rotational band (ν₂ → G) oscillated simultaneously in two pumping cases, i.e. pumping with the R(30) or R(16) line of 9.4 μm band from the CO₂ laser. 26 FIR laser emissions (26.45 μm ～ 281.0 μm) were observed by using 12 different CO₂ laser lines, and the 10 FIR emissions of them may be new laser emissions as far as we know.     

Absolute Intensities of the nu(1) and nu(3) Bands of (16)O(3)

New experimental data on the nu(1) and nu(3) bands of (16)O(3) improving the value of absolute line intensities have been obtained. The intensities of 295 lines have been measured with an average accuracy between 2.5% and 3% and the rotational expansion of the transition moment operators for the nu(1) and nu(3) bands has been deduced. Finally, a complete listing of line intensities has been computed with an intensity cutoff of 1x10(-25) cm(-1)/molecule cm(-2). Copyright 2001 Academic Press.     

Diode-Laser Jet Spectra and Analysis of the nu(1) and nu(4) Fundamentals of CCl(3)F

High-resolution infrared spectra have been measured for mixtures of CCl(3)F in Ne, expanded in a supersonic planar jet. We present the first analysis for the nu(4) fundamental and a complete analysis for the nu(1) band. Accurate spectroscopic constants have been obtained for both the nu(1) fundamental of the most abundant isotopic species, C(35)Cl(3)F, C(35)Cl(2)(37)ClF, and C(35)Cl(37)Cl(2)F. With respect to an earlier work [M. Snels, A. Beil, H. Hollenstein, M. Quack, U. Schmidt, and F. D'Amato, J. Chem. Phys. 103, 8846-8853 (1995)], the observation of Q branches of the three most abundant isotopomers allowed for an unambiguous determination of the nu(1) band origins. The nu(4) fundamental has not been the subject of a high-resolution analysis up to now. The observation of high-resolution spectra of the central part of the band permitted the determination of band origin, rotational constants, and Coriolis constant for the symmetric-top species, C(35)Cl(3)F. Copyright 2001 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.     

Absolute Intensities Measurements in the nu(4) + nu(5) Band of (12)C(2)H(2): Analysis of Herman-Wallis Effects and Forbidden Transitions

We measured absolute line intensities in two bands of (12)C(2)H(2) near 7.5 μm, namely the nu(4) + nu(5)(Sigma(+)(u))-0(Sigma(+)(g)) and nu(4) + nu(5)(Delta(u))-0(Sigma(+)(g)) bands, using Fourier transform spectroscopy with an accuracy estimated to be better than 2%. Using theoretical predictions from Watson [J. K. G. Watson, J. Mol. Spectrosc. 188, 78 (1998)], the observation of the forbidden nu(4) + nu(5)(Delta(u))-0(Sigma(+)(g)) band and the Herman-Wallis behavior exhibited by its rotational lines were studied quantitatively in terms of two types of interactions affecting the levels involved by the band: l-type resonance and Coriolis interaction. In the case of the nu(4) + nu(5)(Sigma(+)(u))-0(Sigma(+)(g)) band, the influence of l-type resonance is also confirmed. We also attributed the intensity asymmetry observed between the R and P branches of that latter band to a Coriolis interaction with l = 1 levels. We did not observe the nu(4) + nu(5)(Sigma(-)(u))-0(Sigma(+)(g)) band, consisting only of a Q branch, in agreement with Watson's prediction. Copyright 2000 Academic Press.     

The Mystery of a Band Vanishing upon Isotopic Substitution: The Case of the v(3) = 1 State of FClO(3)

F. Meguellati, G. Graner, K. Burczyk, and H. Bürger [J. Mol. Spectrosc. 185, 392-402 (1997)] reported in their paper on nu(3)(A(1)) bands of the (35,37)Cl and (16,18)O isotopomers of FClO(3) that the nu(3) bands, which, although weak, could be well observed for the (16)O isotopomers, disappear almost completely in the spectra of the (18)O isotopomers. Because the A and B values for the (18)O isotopomers are so similar that these molecules are very close to spherical tops, much closer than the values for the (16)O species, disappearance of the band was ascribed to selection rules for tetrahedral molecules, the A(1) vibrations of which are inactive. Alternative explanations are proposed in this paper and analyzed. The most likely explanation is that a coincidence among the intensity parameters is responsible for a very low value of the dipole moment derivative; a weak Fermi resonance with the (v(6) = 2, l = 0) state may also participate in the final total wipeout of the band. It is believed that the last mechanism may be of more general interest. 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.     

High-Resolution Study of Strongly Interacting Vibrational Bands of HDO in the Region 7600-8100 cm(-1)

The high-resolution Fourier transform spectrum of the HDO molecule was recorded and analyzed in the region 7600-8100 cm(-1) where the weak vibration-rotation bands 3nu(1) and nu(1) + nu(2) + nu(3) are located. Because of the presence of strong local resonance interactions, transitions belonging to the 3nu(2) + nu(3) and 6nu(2) bands were assigned as well. Spectroscopic parameters of all four bands were estimated, which reproduce initial line positions with accuracy close to experimental uncertainties. 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   

Absolute Line Intensities in the 2nu(0)(2) Band of Cyanogen Chloride at 12.8 µm

Absolute line intensities were measured at high resolution with a tunable diode laser. This work concerns the 2nu(0)(2) band of cyanogen chloride ClCN in the region 780 cm(-1). Thirty-two absorption lines were recorded for the isotopomer (35)ClCN and 26 lines for (37)ClCN. From the analysis of these lines, we determined the bandstrengths: S(0)(v) = 19.14 cm(-2) atm(-1) for (35)ClCN and S(0)(v) = 17.84 cm(-2) atm(-1) for (37)ClCN. Copyright 2000 Academic Press.     

Spectral properties of gaseous biomarkers and choice of the optimal analytical line at interference of the spectra of detected gases

A method for comparative investigation of the absorption line properties at interference of vibration-rotation bands of the detected and interfering gases is proposed. This method is intended for highly sensitive analysis of complex gas mixtures when measurement of absorption in a weak analytical line is hindered by a stronger, closely located interfering line. Disappearance of the analytical line extrema in the spectrum studied is proposed as an assessment criterion. The concentration ratio of the analytical and interfering gases under this condition could be used for quantitative analysis and comparison of the properties. This criterion can be applied to the first and second derivatives of the absorption spectra. To demonstrate the potential of the approach proposed, it was applied to the NO and NH₃ lines that are promising for monitoring the contents of these compounds in atmospheric and exhaled air. The interference of the absorption bands of H₂O, CO₂, and several gaseous biomarkers was analyzed in the near-IR spectral region using the HITRAN2000 database. It was demonstrated that the problem of the vibration-rotation band interference for detected and interfering gases is aggravated in this spectral region. This aggravation is caused not only by the decrease in the absolute band intensity for overtones and combination bands of the molecular vibrations but also by the relative increase in the absorption in H₂O lines and high density of CO₂ lines in the near-IR spectral region.     

Pressure broadening and shift of transitions of the first overtone of HCl

High-resolution spectroscopic measurements were made using distributed feedback diode lasers. We measured line strength and pressure-induced broadening and shift for two lines, R(3) and P(4), of the first overtone (2?0) ro-vibrational band, for the two isotopomers H³⁵Cl and H³⁷Cl, according to their natural abundances; measurements were also made in the presence of foreign gases. Comparison was made with available data when possible. Received: 29 February 2000 / Published online: 8 November 2000     

Far-Infrared Laser Magnetic Resonance Spectroscopic Study of the nu(2) Bending Fundamental of the CCN Radical in Its &Xtilde;(2)Pi(r) State

Bending vibration-rotation transitions between the (010) μ(2)Sigma(-) and (000) (2)Pi(r) vibronic states of the CCN radical in its ground electronic state have been observed using far-infrared laser magnetic resonance (FIR LMR) spectroscopy. Thirteen FIR laser lines were used to record 769 resonances. The LMR data, combined with previous data, were used to determine vibrational, Renner-Teller, fine-structure, rotational, hyperfine, and molecular g-factor parameters using a least-squares fitting routine. The model used was an N(2) effective Hamiltonian modified to include the Renner-Teller effect explicitly in a (2)Pi electronic state. The band origin for the (010) μ(2)Sigma(-) <-- (000) &Xtilde;(2)Pi(r) transition was determined to be 179.598176 +/- 0.000067 cm(-1). The spin-orbit splitting in the ground state was refined and the complete set of (14)N-hyperfine parameters determined for the first time.     

Spectroscopy of the excited C-O stretching Q branch of 13CD3OH: Measurement and assignment of new FIR laser lines

The Q branch of the C-O stretching fundamental band of ¹³CD₃OH has been investigated. Starting from a high resolution (4 × 10⁻³cm⁻¹) infrared Fourier transform spectrum and using a waveguide CO₂ laser of 300 MHz tunability and an acoustooptic modulator for an extension of ±90 MHz, 31 new FIR laser lines have been observed. The related absorptions have been measured by means of optoacoustic detection. The frequency of one new FIR laser line was also measured. Eight tentative assignments are proposed for the IR absorption and FIR laser emissions.     

High-Resolution Fourier Transform Spectra of HDSe: The Interacting States (v(1) v(2) v(3))/(v(1) +/- 1 v(2) -/+ 2 v(3)) with 2v(1) + v(2) = 1, 2, 3, and 4

For the first time, high-resolution Fourier transform spectra of HDSe in the region of the three polyads, nu(1)/2nu(2), nu(1) + nu(2)/3nu(2), and 2nu(1)/nu(1) + 2nu(2)/nu(2) + nu(3), have been recorded and analyzed. Combined with an earlier investigation of the nu(2) band, and including estimates for the unobserved "dark" 4nu(2) band, these levels were subjected to a "Global Fit," which makes use of relations between parameters within the different polyads. Since there are five isotopic species present in natural HD(M)Se (M = 82, 80, 78, 77, 76), altogether 34 vibration-rotation bands have been studied in the present contribution. The parameters determined by the Global Fit reproduce upper vibrational-rotational energies of all these bands with accuracies close to experimental precision. Copyright 2000 Academic Press.