Diode-Laser Measurements of N(2)-Broadening Coefficients in the nu(7) Band of C(2)H(4)

N(2)-broadening coefficients have been measured for 35 lines of C(2)H(4) in the nu(7) fundamental transition, using a tunable diode-laser spectrometer. These lines with 3 相似文献   

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.     

Stark broadening measurements of some N(II) and N(III) lines

The Stark widths of seventeen N(II) and ten N(III) spectral lines, emitted from a wall-stabilized arc plasma with electron densities in the range 0.9-2.9 × 10¹⁷ cm^-3, were measured. The arc was run with a 1:1N₂:He mixture, and the electron densities were determined from the Stark widths of He(I) 5876 and 6678 A. The Stark widths of the N lines were found to scale approximately linearly with electron density.     

Air- and N(2)-Broadening Parameters of Water Vapor: 604 to 2271 cm(-1)

High-resolution measurements of air- and N(2)-broadened widths and pressure-induced frequency shifts of water vapor were obtained covering the spectral region between 604 and 2271 cm(-1). Over 1300 vibration-rotation transitions were measured including the (000)-(000), (010)-(010), (010)-(000), (020)-(010), and (100)-(010) vibrational bands of H(2)(16)O. Also included were measurements of H(2)(18)O and H(2)(17)O from normal water vapor samples and H(2)(18)O + N(2) observations with oxygen-18-enriched gas samples. Collision-narrowing effects were observed in a few lines involving high J and low K(a) transitions with the lowest measured linewidth coefficient equal to 0.0057(4) cm(-1)/atm (air-broadening) for the completely overlapping transitions, 17 0 17 <-- 18 1 18 and 17 1 17 <-- 18 0 18, at 1235.204 cm(-1). The majority of the linewidth values were derived from the measurements using a Voigt line profile. A few lines with air- or N(2)-broadened half-width values of about 0.012 cm(-1) or less were found to exhibit collision-narrowing effects and were also analyzed with a profile proposed by Galatry. The results are compared to values given in previous studies. Copyright 2000 Academic Press.     

Pressure Lineshift and Broadening Coefficients in the 2nu(3) Band of (16)O(12)C(32)S

In this study we report the first measurements of the pressure-induced lineshift coefficients due to Ar, He, O(2), and N(2) for 22 rovibrational lines from P(53) to R(53), belonging to the 2nu(3) band of (16)O(12)C(32)S at 4100 cm(-1). The lineshift results were obtained from the simultaneous record of the pressure-broadened and pure low-pressure OCS lines, using a tunable difference-frequency laser spectrometer. For four lines of the 2nu(3) band we also report Ar-, He-, O(2)-, and N(2)-broadening coefficients by fitting Voigt and Rautian profiles to the measured shapes of these lines. The broadening and shift coefficients are compared to the results of theoretical calculations based on the semiclassical Robert-Bonamy formalism and two different isotropic and anisotropic intermolecular potentials. For OCS-Ar we also consider the Smith-Giraud-Cooper model including all orders of the interaction within the peaking approximation. In all cases, the calculated broadening coefficients are in reasonable agreement with the experimental data. By considering adjustable parameters for the vibrational dependence of the isotropic potential, the general trends of the lineshifts with J can be roughly predicted, except at low J values where an asymmetry behavior for P and R branches is generally observed. Copyright 2000 Academic Press.     

Line-Mixing Effects in He- and N(2)-Broadened Sigma <-- Pi Infrared Q Branches of C(2)H(2)

Two Q branches of C(2)H(2) near 716.3 and 719.9 cm(-1) belonging to the (nu(4) + nu(5))(0) - nu(1f)(4) and 2nu(0)(5)-nu(1f)(5) bands, of Sigma <-- Pi symmetry, have been studied for He and N(2) perturbers at pressures ranging from 0.05 to 1 atm, using a tunable diode-laser spectrometer. To interpret the line-mixing effects observed in these spectra, we have applied a model based on the energy-corrected sudden approximation whose parameters have been only derived from line-broadening data. This model provides satisfactory agreement with experimental bandshapes for both bands and perturbers, especially at pressures higher than 0.1 atm. The Q-branch profiles for C(2)H(2)-He are higher and narrower than those obtained for C(2)H(2)-N(2) at the same pressure as the result of smaller broadening coefficients and larger line-mixing effects in the former system. Copyright 2000 Academic Press.     

Peptide internal motions on nanosecond time scale derived from direct fitting of (13)C and (15)N NMR spectral density functions

NMR relaxation-derived spectral densities provide information on molecular and internal motions occurring on the picosecond to nanosecond time scales. Using (13)C and (15)N NMR relaxation parameters [T(1), T(2), and NOE] acquired at four Larmor frequencies (for (13)C: 62.5, 125, 150, and 200 MHz), spectral densities J(0), J(omega(C)), J(omega(H)), J(omega(H) + omega(C)), J(omega(H) - omega(C)), J(omega(N)), J(omega(H) + omega(N)), and J(omega(H) - omega(N)) were derived as a function of frequency for (15)NH, (13)C(alpha)H, and (13)C(beta)H(3) groups of an alanine residue in an alpha-helix-forming peptide. This extensive relaxation data set has allowed derivation of highly defined (13)C and (15)N spectral density maps. Using Monte Carlo minimization, these maps were fit to a spectral density function of three Lorentzian terms having six motional parameters: tau(0), tau(1), tau(2), c(0), c(1), and c(2), where tau(0), tau(1) and tau(2) are correlation times for overall tumbling and for slower and faster internal motions, and c(0), c(1), and c(2) are their weighting coefficients. Analysis of the high-frequency portion of these maps was particularly informative, especially when deriving motional parameters of the side-chain methyl group for which the order parameter is very small and overall tumbling motions do not dominate the spectral density function. Overall correlation times, tau(0), are found to be in nanosecond range, consistent with values determined using the Lipari-Szabo model-free approach. Internal motional correlation times range from picoseconds for methyl group rotation to nanoseconds for backbone N-H, C(alpha)-H, and C(alpha)-C(beta) bond motions. General application of this approach will allow greater insight into the internal motions in peptides and proteins.     

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.     

Air pressure broadening and shifting of high-J lines of (00011) ← (00001) band of CO2

The absorption spectra of carbon dioxide (isotope 626, natural abundance in air, ambient temperature) have been studied at total pressures 68-570 Torr with spectral resolution 0.003-0.005 cm⁻¹. The spectra were measured in the spectral domain of 2273-2393 cm⁻¹ by FTIR spectrometer Bruker IFS 125 HR equipped with White-type multipass cell (6.4-41.6 m) and with a cell having 10 cm optical path length. Pressure broadening and shift coefficients were obtained from a series of spectra by means of a nonlinear least-squares spectral fitting technique for the lines of the (00011)←(00001) band with rotational quantum number up to J=82. For fitting of the individual line shapes, we used the Voigt profile with pre-calculated Doppler broadening parameter. The experimental pressure broadening and shift coefficients are compared with the values available in spectroscopic databases HITRAN 2008 and Carbon Dioxide Spectroscopic Databank (CDSD-296) and with other experimental values reported in the literature.     

The Dynamics of N(2)-O(3) and N(2)-SO(2) Probed by Microwave Spectroscopy

The microwave spectra of N(2)-O(3) and N(2)-SO(2) have been recorded in the 6-18 GHz range using a pulsed-nozzle, Fourier transform microwave spectrometer. C-type transitions have been observed for both complexes which are slightly shifted by internal tunneling motions of the O(3) or SO(2) moieties. In addition, unshifted a-type transitions have been observed for N(2)-O(3). The nuclear hyperfine pattern is typical of equivalent nitrogen nuclei. Two sets of rotational and hyperfine constants are required to fit the symmetric and antisymmetric nuclear spin states, indicating that the equivalence arises from tunneling rotation of the nitrogen molecule. Internal tunneling motions along three tunneling pathways have been identified, although no information on the N(2) tunneling frequency is available from the spectra. From the N(2)-O(3) data the tunneling frequencies cannot be decorrelated from the rotational parameters; however, the O(3) tunneling frequency upper limit is estimated to be 2.0 MHz and the frequency of the concerted tunneling motion of both moieties is estimated to be about 8.9 MHz. For N(2)-SO(2), the SO(2) tunneling frequency is 11.5 kHz and the concerted frequency 173.9 kHz. Both complexes are roughly T shaped with the N(2) axis approximately perpendicular to the O(3) or SO(2) plane. In the equilibrium structures of both complexes, the a-c inertial plane is a plane of symmetry. The centers of mass separations are estimated from the rotational parameters to be 3.582 ? for N(2)-O(3) and 3.875 ? for N(2)-SO(2). The angle between the symmetry axes of the O(3) or SO(2) and the line joining their centers of mass have been calculated as 130.84 degrees (or 49.16 degrees ) and 119.71 degrees (or 60.29 degrees ), respectively. From the quadrupole analysis, the average angle between the N(2) axis and the a-inertial axis is 32.12 degrees for N(2)-O(3) and 27.81 degrees for N(2)-SO(2). Model electrostatic and ab initio calculations confirm these structures. Differences between the experimental and calculated structural parameters highlight the role of tunneling dynamics in these complexes. Copyright 2000 Academic Press.     

Cs(6P)+(Ne,N2)碰撞能量转移

在气体样品池条件下,研究了Cs(6P3/2) (Ne,N2)碰撞能量转移过程.用调频半导体激光器激发Cs原子至Cs(6P3/2)态,在不同的Ne或N2气压下,测量了直接6P3/2→6S1/2荧光和转移6P1/2→6S1/2荧光,对于6P3/2与Ne的碰撞,电子态能量仅能转移为Ne原子的平动能.在与N2的碰撞中,向分子振转态的转移是重要的.利用速率方程分析,可以得到碰撞转移速率系数,对于Ne,6PJ精细结构碰撞转移速率系数为1.45×10-12cm3·s-1.对于N2,测量6P Ne和6P N2二种情况下荧光的相对强度比,确定精细结构速率系数为1.64×10-12cm3·s-1,6P态猝灭速率系数为4.88×10-12cm3·s-1.     

Analysis of High-Resolution Spectra of (18)O(3)

Using a Fourier transform spectrometer, we have recorded the spectra of the (18)O(3) species of ozone in the region 1300-3100 cm(-1), with a resolution of 0.003 cm(-1). The large product pathlength x pressure enable us to record 18 bands, 14 for the first time. The analysis has been performed using effective Hamiltonians for polyads of strongly interacting states for ozone, accounting for Coriolis and anharmonic resonances. The spectral parameters are derived for 16 vibrational states, including the two "dark" states (040) and (130). Various resonances are studied through the mixing coefficients of rovibrational wavefunctions. Systematic intensity measurements allow determination of transition moment parameters for 16 bands. Finally, a complete list of all transitions from 1300 to 3100 cm(-1), with cutoffs 10(-26) cm(-1)/mol cm(-2) (296 K), is calculated. Copyright 2001 Academic Press.     

Ar- and air-broadening coefficients in the ν3 band of CS2 at room and low temperatures

Using a diode-laser spectrometer, Ar-broadening coefficients for 16 spectral lines in the fundamental ν₃ band of CS₂ have been measured at five temperatures: 298.0, 273.2, 248.2, 223.2 and 198.2 K. These lines with J values ranging from 2 to 64 are located in the spectral range 1519-1547 cm⁻¹. The broadening coefficients are also calculated from a semiclassical impact model performed by using a simple empirical intermolecular potential. From the theoretical and experimental results obtained at the different temperatures, we have determined the n exponent values governing the temperature dependence of the broadening coefficients. The air-broadening coefficients for four spectral lines in the ν₃ band of CS₂ have also been measured experimentally at the same temperatures. They are compared to the values derived from those obtained previously for the perturbers N₂, O₂ and also Ar.     

Measurements of relative line strengths in N I multiplets for transition arrays 3s-np (n=3, 4, 5)

Applying the emission method, intensities of 60 spectral lines of neutral nitrogen (N I) belonging to 15 multiplets originating from 3s-np (n=3, 4, 5) transition arrays have been measured. A wall-stabilized arc, operated at atmospheric pressure in helium with some admixture of nitrogen was applied as the excitation source. From measured line intensities, relative line strengths within multiplets have been evaluated. For transitions with Δn=1 and 2, significantly larger discrepancies from LS coupling results are found if compared to transitions 3s-3p (Δn=0). The measured relative line strengths within 3s-3p multiplets are compared with older measurements, recent calculations and with the new data recommended by NIST.     

N2-broadening coefficients of methyl chloride at room temperature

Methyl chloride is of interest for atmospheric applications, since this molecule is directly involved in the catalytic destruction of ozone in the lower stratosphere. In a previous work [Bray et al. JQSRT 2011;112:2446], lines positions and intensities of self-perturbed ¹²CH₃³⁵Cl and ¹²CH₃³⁷Cl have been studied into details for the 3.4 μm spectral region. The present work is focused on measurement and calculation of N₂-broadening coefficients of the ¹²CH₃³⁵Cl and ¹²CH₃³⁷Cl isotopologues. High-resolution Fourier Transform spectra of CH₃Cl–N₂ mixtures at room-temperature have been recorded between 2800 and 3200 cm^?1 at LADIR (using a classical source) and between 47 and 59 cm^?1 at SOLEIL (using the synchrotron source on the AILES beamline). 612 mid-infrared transitions of the ν₁ band and 86 far-infrared transitions of the pure rotational band have been analyzed using a multispectrum fitting procedure. Average accuracy on the deduced N₂-broadening coefficients has been estimated to 5% and 10% in the mid- and far-infrared spectral regions, respectively. The J- and K-rotational dependences of these coefficients have been observed in the mid-infrared region and then a simulation has been performed using an empirical model for 0≤J≤50, K≤9. The ¹²CH₃³⁵Cl–N₂ line widths for 0≤J≤50 and K≤10 of the ν₁ band and for 55≤J≤67 and K≤15 of the pure rotational band have been computed using a semi-classical approach involving exact trajectories and a real symmetric-top geometry of the active molecule. Finally, a global comparison with the experimental and theoretical data existing in the literature has been performed. Similar J- and K-rotational dependences have been appeared while no clear evidence for any vibrational or isotopic dependences have been pointed out.     

Trend of lower stratospheric methane (CH4) from atmospheric chemistry experiment (ACE) and atmospheric trace molecule spectroscopy (ATMOS) measurements

The long-term trend of methane (CH₄) in the lower stratosphere has been estimated for the 1985-2008 time period by combining spaceborne solar occultation measurements recorded with high spectral resolution Fourier transform spectrometers (FTSs). Volume mixing ratio (VMR) FTS measurements from the ATMOS (atmospheric trace molecule spectroscopy) FTS covering 120-10 hPa (∼16-30 km altitude) at 25°N-35°N latitude from 1985 and 1994 have been combined with Atmospheric Chemistry Experiment (ACE) SCISAT-1 FTS measurements covering the same latitude and pressure range from 2004 to 2008. The CH₄ trend was estimated by referencing the VMRs to those measured for the long-lived constituent N₂O to account for the dynamic history of the sampled airmasses. The combined measurement set shows that the VMR increase measured by ATMOS has been replaced by a leveling off during the ACE measurement time period. Our conclusion is consistent with both remote sensing and in situ measurements of the CH₄ trend obtained over the same time span.     

High-Resolution Laser Spectroscopy of YbCl: The A(2)Pi-X(2)Sigma(+) Transition

The A(2)Pi-X(2)Sigma(+) transition of (174)Yb(35)Cl and (172)Yb(35)Cl has been rotationally analyzed for the first time. Doppler-limited laser excitation spectroscopy with selective detection of fluorescence was used to obtain spectra of the 0-0 and 1-0 bands with a measurement accuracy of approximately 0.0035 cm(-1). Resolved fluorescence was used to record the 0-1, 0-2, and 0-3 bands and to unequivocally assign the rotational numbering, N, to the laser excitation spectra. In total, over 1300 line positions have been measured and assigned for each of the two isotopomers and employed in least-squares fits of molecular parameters. The principal results for the A(2)Pi state are A(e) = 1491.494(2) cm(-1) and R(e) = 2.4433(1) ?, and for the X(2)Sigma(+) state, R(e) = 2.4883(2) ? and gamma(e) = 4.59(2) x 10(-3) cm(-1). The interaction between the X(2)Sigma(+) and A(2)Pi states has been investigated and is shown to be the main contributor to the spin-rotation splitting in the ground state. Copyright 2000 Academic Press.     

Collisional broadening and line intensities in the ν2 and ν4 bands of PH3

Using a tunable diode-laser spectrometer self-broadening coefficients and absolute intensities have been measured for 26 lines of PH₃ at 298 K in the QR branch of the ν₂ band and the PP and RP branches of the ν₄ band. The recorded lines with J values ranging from 2 to 14 and K from 0 to 11 are located in the spectral range 995-1093 cm⁻¹. Self-broadening coefficients have also been measured at 173.4 K for nine of these lines. The collisional widths and line strengths are obtained by fitting each spectral line with different theoretical profiles. The results obtained for the line intensities are in good agreement with recent measurements [J. Mol. Spectrosc. 215 (2002) 178]. The self-broadening coefficients are also calculated on the basis of a simple semiclassical model involving only the electrostatic interactions. A satisfactory agreement is obtained except for high J values or K values equal to J, for which the calculated results are notably underestimated. By comparing broadening coefficients at room and low temperatures, the temperature dependence of these broadenings has been determined both experimentally and theoretically.     

Ar-Broadening of isotropic Raman lines in the ν2 band of acetylene

Using a high resolution Raman spectrometer, we have measured Ar-broadening coefficients in the ν₂Q branch of C₂H₂ for 22 lines at 295 K, 20 lines at 174 K, and 16 lines at 134 K. These lines with J values ranging from 1 to 23 are located in the spectral range 1970.9-1974.3 cm⁻¹. The collisional widths are obtained by fitting each spectral line with a Rautian profile. The resulting broadening coefficients are compared with theoretical values arising from close coupling and coupled states calculations. A satisfactory agreement is obtained at room as well as at low temperatures, especially for odd J lines. By comparing broadening coefficients at 295, 174, and 134 K from a simple power law, the temperature dependence of these broadenings has been determined both experimentally, and theoretically.     

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.