Water vapor overtones pressure line broadening and shifting measurements

By using a spectrometer having as source a commercial etherostructure Al _x Ga_{1 − x} As diode laser operating in “free-running mode”, line shape parameters of some water vapor ro-vibrational overtones at 820–830 nm have been measured at room temperature. These weak absorption lines have been detected by using the wavelength modulation spectroscopy technique with second-harmonic detection. The broadening and shifting coefficients have been obtained by fitting the collected second-harmonic absorption features while varying the pressure of different foreign gases.     

Foreign gas broadening of difluoromethane by N2, O2 and CO2

The linewidth parameters of difluoromethane broadened by N₂, O₂, and CO₂ have been measured at microwave frequencies and are compared with calculated values for dipole-quadrupole interactions by using the Murphy-Boggs theory. The observed linewidths yield reasonable values of molecular quadrupole moments.     

Calculations of ozone line shifting induced by N2 and O2 pressure

Ozone line shifts by nitrogen and oxygen pressure are computed for the ν₁ + ν₃, 2ν₁ and 2ν₃ bands of the 5 μm spectral region by a semiempirical approach. The calculated values agree with measurements better than 0.001 cm^?1 atm^?1 for 98% of O₃–N₂ lines and 87% of O₃–O₂ lines. In contrast with the water molecule case, the polarization components of the interaction potential are shown to contribute to the line shift more efficiently than the electrostatic interactions. As intermediate results, the mean dipole polarizability and the components of the polarizability tensor for the vibrational states (101), (200), and (002) of ozone molecule are determined by least-squares fitting of theoretical shifts to some experimental values. The temperature exponents for the ν₁ + ν₃ band lines are also estimated.     

Collisional line shifting and broadening in the fundamental P-branch of CO in Ar between 214 and 324 K

The collisional shifts and widths of several P-branch spectral lines in the fundamental band of CO-Ar have been measured at temperatures between 214 and 324 K and pressures between 0.025 and 1 atm. The widths have been determined using a line shape model based on the solution of the transport/relaxation equation for the appropriate off-diagonal element of the density matrix. The model uses a realistic molecular potential energy surface to calculate the speed dependence of the collisional broadening, and a rigid sphere potential to calculate the translational motion. It is found that both the shifting and broadening coefficients follow a power law dependence on the temperature. Additionally, it is demonstrated that studies have tended to overestimate the accuracy of collisional widths when the line shape model used to obtain the widths involves multiple fitted line shape parameters or fails to fit the measured spectra within the experimental noise.     

Simultaneous determination of the ground level abundances of N2O,CO2, CO and H2O

The AFCRL atmospheric line-parameter listing has been used with a non-linear, least-squares method of analysis to obtain the abundances of N₂O and CO in a sample of ground level air with a precision of about 1%. Absorption coefficients calculated for N₂O agree satisfactory with laboratory measurements but an error of 0.0267 cm^-1 in the listed position of an H₂O line at 2205.250 cm^-1 has been corrected and errors in the positions and intensities of CO₂ lines between 2230 and 2250 cm^-1 have been observed.     

A new calculation for line broadening of Lyman-α in plasmas

A line-shape calculation of Ly-α is presented which uses a new method based on operator-valued temporal correlation functions.     

Real-gas properties of n-alkanes, O2, N2, H2O, CO, CO2, and H2 for diesel engine operation conditions

The objective of the research outlined in this paper was to develop the analytical approximations for calculating real-gas properties (p-v-T data, thermodynamic functions: internal energy, enthalpy, and entropy, and specific heats) of vapor-phase n-alkanes from C₁ (methane) to C₁₄ (normal tetradecane), O₂, N₂, H₂O, CO, CO₂, and H₂ within the range of pressure 0.05 MPa ≤ p ≤ 20 MPa and temperature 280 K ≤ T ≤ 3000 K aimed for implementation into computational fluid dynamics (CFD)-codes simulating the operation process in modern Diesel engines. The analytical approximations have been developed based on available literature data and on the new equation of state for moderately dense gases. The approximations reported are rather simple and therefore can be used directly in CFD codes. Approximations for mixing rules are also provided.     

High-resolution measurements of line intensity, broadening and shift of CO around m

Fundamental spectroscopical parameters of CO₂ are reported using a high resolution, direct absorption spectrometer, based on a distributed feed-back diode laser emitting at 2 μm. Line intensity, self- and foreign broadening and shift, with N₂ and O₂ as foreign gases, have been measured with high accuracy in the combination band of CO₂, for 13 lines of the R branch, from R(22) up to R(46). Comparison with available data is made, when possible, and a generally good agreement has been found. Received: 24 April 1998 / Received in final form: 28 October 1998     

Pressure shift and/or broadening of lines in the electronic spectra of Cl2, Br2, I2, O2, HD,AlH and H2CO

Line positions and widths of the B³Π_o⁺u?X¹Σ⁺_g electronic transitions of chlorine and bromine gases are measured in absorption as functions of pressure by means of a scanning Fabry-Perot interferometer spectrometer (resolving power > 10⁶). No dependences on quantum numbers are detected. Deconvolutions of measured full-widths-at-half-maxima (FWHM) reveal collision broadening for pressures between 1 and 225 torr. The ratio of self-broadening to shift is always less than that expected for a van der Waals interaction in the impact approximation, namely -2.77. Accordingly, the Lennard-Jones potential is used to determine the effect of the electronic transitions on C₆ and C₁₂, and there are found 14 and 6% changes in C₆ for Cl₂ and Br₂, respectively. If, instead, one uses the self-broadening only, and a pure van der Waals interaction, the changes are 6 and 5%. Because the effects are in either model unexpectedly small, comparisons are made with less complete measurements (from the literature) for self-broadening in I₂, the B¹Σ⁺_g?X³Σ^-_g system of O₂ and the B^′Σ⁺_g?X¹Σ⁺_g system of HD, and for foreign-gas broadening in the A¹Π?X¹Σ system of A1H and the A̋¹A₂(π¹, n)?X̋¹A₁ system of H₂CO as well as the HD system.     

Collisional broadening and shifting of OCS rotational spectrum lines

Broadening and shifting of carbonyl sulfide (OCS) rotational spectrum lines by pressure of N₂, O₂ and OCS were accurately studied in the frequency range 24–850 GHz at room temperature using a spectrometer with radio-acoustic detection of absorption. Rotational dependences of collisional widths of OCS spectrum lines were determined by a simple empirical polynomial fit of experimental data. Experimental uncertainties were analyzed. Results of supplementary test measurements of self-broadening of rotational OCS lines in the ν₂ excited vibrational state and carbon monoxide (CO) lines in the ground vibrational state are presented. Comparison of the obtained results with previously known measurements and theoretical calculations is given. The performed work allows for the first time development of accurate gaseous etalon of absorption for atmospheric applications and laboratory use, covering continuously the whole millimeter- and submillimeter-wave range.     

Quantum mechanical calculation of Suryan’s line broadening in nuclear magnetic resonance

The first quantum theory of the classical radiation damping in nuclear magnetic resonance is presented. Relaxation times and life times arising from the interaction of nuclear spin with the radio-frequency radiation field are calculated. Second-order line shifts are predicted and the existence ofI _z andI _z ² -type operators due to photons is pointed out. The predicted line shifts as well as relaxation are found to be measurably large. Numerical estimates are given for protons in water.     

Line parameter measurements and calculations of CO broadened by H2O and CO2 at elevated temperatures

Measurements of collisional broadening of four fundamental CO lines in atmospheres of CO₂ and H₂O at 300–600 K were made. The Voigt line-shape model was fitted parametrically to the absorption spectra line-shapes. The results are compared with other experimental studies and with theoretical calculations for CO₂ broadening. Absorption spectra of the exhaust gases of a flat flame were recorded and analyzed to yield CO concentration, temperature, and line half-widths. The flame spectra half-widths were compared with extrapolations of lower temperature data using the simple power law approximation $\text{γ(T)=γ(T}{}_0\text{) (}\text{T}{}_0\text{T}\text{)}{}^{\mathrm{n}}$. The utility of this approximation in the development of combustion diagnostic techniques is discussed.     

Angular distribution of the photoelectron spectrum of CO2, COS,CS2, N2O,H2O,and H2S

The photoelectron spectra of the triatomic molecules CO₂, COS, CS₂, N₂O, H₂O, and H₂S have been measured as a function of the angle θ between the direction of the incoming photon and outgoing photoelectron. The photoelectron spectra have been measured with a double-focusing electrostatic electron spectrometer to which has been attached a chamber containing a gas discharge lamp that can be freely rotated. (The photon source used was the 21.22 eV He I resonance line). From the dependence of intensity as a function of θ the angular parameter β was determined for each ionization band observed in the photoelectron spectra. A correlation was noted between the values of β and the molecular orbitals relative to the contributions of oxygen and sulfur atomic orbitals. Individual β values were also obtained for most of the vibrational bands seen in the photoelectron spectra. In most cases the vibrational structure showed little or no change in the angular parameter for a given electronic state. In certain cases, however, such as the fourth ionization band in CS₂, CO₂, and COS, rather sizeable changes in β were observed for the different vibrational bands.     

Vibrationally inelastic scattering of H∼ ions from H2, N2, O2 and CO2

State-resolved measurements are presented for vibrational excitation of H₂, N₂, O₂ and CO₂ by H^? impact in the collision energy rangeE _cm=20–180 eV and for scattering in the forward direction (0±0.5°). The data obtained from the measurements are the relative intensities and differential cross sections for vibrational excitation up toν′=4, the transition probabilitiesP _0→ν′ and the vibrational energy transferΔE _vib. For the systems H^?-H₂, N₂, O₂ the vibrational inelasticity increases in the order H₂-N₂-O₂. The mechanism for vibrational excitation in these systems is due to transient charge transfer from the H^? ion into antibonding orbitals of the target molecule which provides a bond stretching force during the collision. For H₂ and N₂, the results are compared with corresponding measurements for H⁺ scattering where the interaction mechanism is quite different. In the case of CO₂, vibrational excitation in forward scattering is caused primarily by the long-range dipole interaction. The spectra are very similar for H^?-CO₂ and H⁺-CO₂. Finer details are attributed to the influence of transient charge transfer and valence interactions.     

Rotational dependence of the broadening of lines of the ν2 band of H2O induced by nitrogen pressure

A semiempirical method for calculating the coefficients of broadening of spectral lines of H₂O molecules subjected to nitrogen pressure is developed. The method involves different corrections associated with deviations from the Anderson approximation. The parameters of the method are determined from the adjustment of the coefficients of broadening to experimental data, which makes it possible to predict fairly accurately the parameters of the contour of a line whose measurements were not performed. On the basis of numerous calculations in terms of this method, a numerical analysis is made that allows one to conclude that the rotational dependence of the half-widths of the lines is more complex than was previously believed and to reveal the basic trends of this dependence.     

High resolution measurements of the line positions and strengths of the 2ν2 band of H2CO

Spectra of the 2ν₂ band of formaldehyde have been obtained with high resolution (0.035 cm^?1). Measurements were made with path lengths of 8, 16, and 24 m and at sample pressures from 0.1 to 0.3 mm Hg at room temperature (～296°K). From these data, the following constants were determined for the 2ν₂ band in wavenumber units: v₀=3471.718±0.004,A=9.3958±030013,B=1.28100±0.00024,C=1.11662±0.00024, Tbbb=-12.8±0.5×10^-6,Taabb=60±5×10^-6. The line strengths were also obtained from the data. The strengths were analyzed to determine the band strength and the rotational factors. At 296°K, the strength of the 2ν₂ band was found to be 15.5 ± 0.9 cm^?1/(cm·atm).