Diode laser measurements of the band strengths of ν3 and ν6 in 12CH3D

A diode laser spectrometer has been used to measure line strengths for 143 transitions in the ν₆ fundamental band of ¹²CH₃D near 9 μm. These line-strength measurements have been used to derive a band strength for ν₆ and ν₃. The band strength derived for ν₆ is 61.7 ± 1.8 cm^?2 atm^?1, and that for ν₃ is 49.3 ± 1.4 cm^?2 atm^?1 at 395 K.     

Collision induced absorption spectra of the fundamental band of D2 in binary mixtures D2-Kr at 298 K

The enhancement spectrum of the collision induced absorption of D₂ in its fundamental band region 2600-4000 cm⁻¹ in binary mixtures D₂-Kr was studied at 298 K for base densities of D₂ in the range 9-20 amagat and for partial densities of Kr in the range 7-120 amagat. The binary absorption coefficient of the band has been determined from the measured integrated absorption coefficient and found to be 3.9 × 10⁻³ cm⁻² amagat⁻². An analysis of the experimental spectrum was carried out by assuming appropriate line-shape functions and the half-width parameters δ₁, δ₂, δ_d and δ_c of the long range quadrupole, and of the short range overlap induced transitions have been determined. Good agreement was obtained between the recorded spectrum of the fundamental band and the synthetic profile.     

Strengths and air-broadened widths of H2O lines in the 2950–3400 cm-1 region

Measurements of the strengths and air-broadened widths of 223 lines of water vapor have been made with high resolution in the region 2950–3400 cm^-1. The strength data of the lines in the 2ν₂ and ν₁ bands are analyzed to determine the band strengths and the coefficients of the F factors. The band strengths of the 2ν₂ and ν₁ bands were found to be 1.75±0.08 and 10.3±1.1 cm^-2 atm^-1 at 296 K, respectively. The selection rules of the lines observed in the ν₃ band are forbidden in the symmetric-rotor limit. The majority of the measured strengths of these lines differ from the calculated values because of different asymmetries in the upper and lower vibrational states. Also, Coriolis perturbations in several lines of the ν₁ and ν₃ bands were observed in the strength measurements. The direct method was applied to determine the air-broadened line widths. The results are compared to the computed values of Benedict and Kaplan. There is good agreement between this work and the computed results for line width values greater than 0.05 cm^-1 atm^-1. However, for line widths less than 0.05 cm^-1 atm^-1, the measured values are smaller than the computed widths. A value of 0.018 cm^-1 atm^-1 is given for the width of the line at 3378.071 cm^-1, whereas the calculated value is 0.032 cm^-1 atm.     

Diode laser line strength measurements of the (ν4 + ν5)0 band of 12C2H2

A diode laser spectrometer that was operated in sweep integration mode was used to measure individual line strengths for 17 R-branch transitions of the (ν₄ + ν₅)⁰ combination band of ¹²C₂H₂ at 7.4 μm. Analysis of these results gives a band strength S_v = 64.4 ± 2.0 cm^?2 atm^?1 at 296 K. Line-broadening parameters for several of these transitions were determined by using both N₂ and He as broadening gases.     

Measurements of the HCN ν3 band broadened by N2

N₂-broadened halfwidths have been measured for 51 absorption lines belonging to the ν₃ fundamental band of hydrogen cyanide (¹H¹²C¹⁴N) near 3311 cm^?1. The data were recorded at room temperature using a Fourier transform spectrometer with a nominal resolution of 0.06 cm^?1. A nonlinear least-squares spectral-fitting procedure was used to obtain both line intensities and collision-broadened halfwidths from scans recorded at several different pressures. The N₂-broadened halfwidths, determined for all lines with J ≤ 25 in both the P and R branches of the band, show the expected distribution with J for broadening by a nonpolar gas. The halfwidth values range from approximately 0.17 cm^?1 atm^?1 near the band center to 0.11 cm^?1 atm^?1 for high-J lines. The band intensity for the ν₃ fundamental derived from these measurements is 236.2 ± 9.5 cm^?2 atm^?1 at 296 K, and empirical coefficients for the vibration-rotation interaction F-factor were also determined.     

Intensities of the v1-bands of 12CH335Cl and 12CH337Cl near 3 μm

Strengths of individual lines in the v₁ fundamental of methyl chloride have been measured at low pressure and at 296.35 K using a Fourier transform interferometer. The band strengths S_v⁰ obtained by fitting these measurements are 85.8±1.0 and 86.6±1.0 cm^-2 atm^-1 for ¹²CH₃³⁵Cl and ¹²CH₃³⁷Cl, respectively. The Q₃-branch appears to be useful for atmospheric detection of methyl chloride.     

Some Raman bands of C3O2

The ν₁, ν₅, 2ν₅, and 2ν₆ Raman band accumulations of carbon suboxide, C₃O₂, have been photographed with a resolution of 0.2–0.3 cm^?1. Each band accumulation consists, in addition to the main band, of a large number of “hot” bands due to the extremely low, highly anharmonic ν₇ fundamental vibration. In the 2ν₆ band accumulation a few series of unresolved Q branches have been assigned. In the ν₁ and 2ν₅ band accumulations most Q branches almost coincide, forming a very intense peak, whereas the dominating feature of the ν₅ band accumulation is a minimum, in agreement with the expectation of an extremely weak Q branch for a Π_g fundamental band. Tentative values of ν₁ = 2196.9 ± 0.1 cm^?1 and ν₅ = 580.2 ± 0.5 cm^?1 as well as several energy values in the ν₇ manifold of the 2ν₆⁰ state are obtained. Further, improved exposures of the ν₂ + 2ν₇⁰ band accumulation yield some levels in the ν₇ manifold of the ν₂ state, in addition to those determined previously.     

High-resolution infrared spectrum and rovibrational analysis of the ν3 fundamental of diazirine,H213CN2

The high-resolution infrared spectrum of ¹³C-diazirine was recorded using a high-information Fourier transform spectrometer with a resolution of 0.0054 cm^?1. The rovibrational structure of the ν₃ fundamental at 1458.1884 cm^?1, which is an A-type parallel band (¹³CH₂ deformation) was assigned and analyzed with extensive use of modern methods of spectrum simulation. The rovibrational assignment and the molecular constants determined for the excited vibrational level of this band are given.     

Spectral intensities in the ν3 bands of 12CH4 and 13CH4

Relative and absolute line intensities for the ν₃ bands of the ¹²C and ¹³C isotopic varieties of methane have been measured using a tunable difference-frequency laser spectrometer. From these data the integrated band strength of ¹³CH₄ is calculated to be 0.983 ± 0.007 that of ¹²CH₄, with the uncertainty representing three standard deviations. The absolute ν₃ bandstrength for ¹²CH₄ is 266.1 ± 3.0 cm^?2 atm ^?1 at 294.7 K where the errors are dominated by the pressure measurement. This band strength corresponds to an effective transition moment 〈μ₃〉 = 0.0534(3)D for ¹²CH₄ from which the ν₄ band dipole moment and the Herman-Wallis F factor can be estimated using a recent force field model for methane.     

Spectral intensities of the 4-μm ν1 + ν3 combination band of SO2

The transition intensities of the 4-μm bands of SO₂ are measured with high precision using a tunable laser difference-frequency spectrometer. The band strength calculated from the ν₁ + ν₃ combination band data at 295.2K is S_v⁰ = 10.54 ± 0.04 cm^?2 atm^?1. Here the uncertainty (three standard deviations) quoted is for the relative precision only; the absolute accuracy, which depends on the sample pressure calibration, is ～1%. F-factors and “hot” band results are also obtained.     

Tunable diode laser measurements of spectral parameters of HCN at room temperature

A tunable infrared diode laser was used to record 17 fully resolved vibration-rotation transitions in the v₁ fundamental band of HCN at 3μ. The experiments were conducted in an absorption cell on room temperature mixtures of HCN diluted by N₂ and Ar. The v₁ fundamental band strength of HCN was determined to be 267±8 cm^-2 atm^-1 at 273.2 K. Small but significant reductions in the residual errors were obtained by using the Galatry profile rather than the Voigt profile to fit the experimentally recorded line shapes. Collisional broadening and narrowing parameters were determined simultaneously from Galatry profile fits to the data. The collision-broadened linewidths of HCN lines in N₂ and Ar were determined as a function of rotational quantum number of transitions ranging from P(14) to R(14) (3268.22-3353.29 cm^-1). The optical diffusion coefficients of HCN in N₂ and Ar at 300 K were determined from the collisional narrowing parameters and were 0.074±0.01 and 0.016±0.03 cm²s^-1 respectively.     

Absorption spectra of C6H6 and C6D6 near 340 nm

The absorption spectra of C₆H₆ and C₆D₆ in the liquid phase have been studied near 340 nm. The absorption spectrophotometric mounting was a sequential double-beam attachment with linear response to energy on scanning of the spectrum before the exit slit and an electronic device which gives directly either the absorbance or the integrated absorbance of a transition and, consequently, its oscillator strength.The oscillator strength measured for the band of C₆H₆ is 8×10^?8, which corresponds to a dipole moment of 2.4×10^?3 Debye; this value is of the same order as a theoretical value calculated by Tsubomura and Mulliken (3.8×10^?3 Debye) for a transition between states ³F and ³A of an oxygen-benzene pair. This agreement corroborates the hypothetical existence of such a transition.The first vibrational band is at 28553 cm^?1 for C₆H₆; this band is not observed in the vapor or solid phase. It corresponds probably to the transition 0-0, which is considered in the literature to be near 29500 cm^?1. The isotopic shift measured for this first band is 164 cm^?1. The vibrational frequencies are, respectively, 910 cm^?1 for C₆H₆ and 889 cm^?1 for C₆D₆.     

Magnon Raman scattering in CoBr2

The one-magnon Raman spectrum of CoBr₂ has been investigated as a function of temperature, and peak frequency, integrated intensity and width parameters obtained. The results obtained for the band energy at low temperature (22.2 ± 0.2 cm^-1 at 5.7.K) are in good agreement with AFMR and neutron scattering results. The one-magnon energy renormalises relatively slowly with increasing temperature and is about 15 cm^-1 at T_N = 19 K, whereas the integrated intensity approaches zero like the magnetization at T_N and the width diverges. A low intensity band at 26.8 ± 1 cm^-1 (7.6K) may be due to two-magnon scattering from spin waves along the c-axis.     

The absorption spectrum of CO2 around 7740 cm-1

Absolute intensities of the vibration-rotation lines of the CO₂ 401_II←000 band 7734 cm^-1 are measured under high-resolution, low-pressure conditions by use of a White-type 25-m base-path, absorption cell together with a 5-m Czerny-Turner spectrometer. The total band intensity S_B, the purely vibrational transition moment

, and the vibration-rotation interaction constant ζ are calculated from the intensity measurements. The values obtained for these parameters are S_B(401_II) = (7.06±0.07) × 10^-5 cm^-2 atm^-1_293°K,

= (3.08±0.03)×10^-5 debye, and ζ = (2.5±0.5)×10^-4. The intensity of the associated “hot band” 411_II←010 is also determined and found to be S_B(411_II←010) = (0.53±0.02)×10^-5 cm^-2 atm^-1_293°K.     

Identification and intensities of the “forbidden” 3ν23 band of 12C16O2

Lines of the 3ν₂³ “forbidden” band of ¹²C¹⁶O₂ have been identified in the 2000-cm^?1 region of a long-path, 0.01-cm^?1 resolution laboratory absorption spectrum. This band has detectable intensity due to Δl = 2 Fermi interactions between the upper level and the nearby ν₁ + ν₂ and 3ν₂¹ levels. Intensities of 18 lines of this band have been measured using a nonlinear least-squares spectral fitting technique. The intensities are enhanced at high J and an expression for the intensity distribution as derived by Toth [Appl. Opt.23, 1825–1834 (1984)] is used for the analysis. In terms of the total sample pressure, the vibrational band intensity is 0.194 ± 0.008 × 10^?30 cm^?1/molecule-cm^?2 at 296 K. The coefficient in the F factor is analogous to the Coriolis coefficient ξ and has been determined to be ?0.0413 ± 0.0015. As expected by theory, its value is very close to that of ξ for the related ν₁ + ν₂ band.     

Rotationally resolved electronic spectroscopy of a nonlinear carbon chain radical C6H4

Rotationally resolved electronic spectrum of the origin band in the 2A″-X2A″ transition of a nonlinear carbon chain radical C₆H₄⁺ has been recorded in the 604 nm region using cw cavity ring down spectroscopy. The radical was produced by a discharge through an acetylene-helium mixture in a supersonic planar expansion. The rotational structure has been analysed and precisely determined. A band having a-type prolate rotational structure has also been observed near 581 nm. By considering the results of ab initio calculations this band is assigned to a transition involving the excitation of the ν₁₂ fundamental in the upper 2A″ electronic state of the same C₆H₄⁺ isomer.     

Measurement at different temperatures of absolute intensities,line half-widths,and broadening by Ar and N2 for the 3001II←0000 band of CO2

Absolute intensities, self-broadening coefficients, and foreign-gas broadening by Ar and N₂ were measured at temperatures of 197, 233 and 294 K for the 30⁰1_II←00⁰0 band of CO₂ at 6348 cm^-1. Also, the intensity parameters and total band intensity were calculated. We obtained for the vibration-rotation interaction factor the value F(m) = 1 + (0.26 ± 0.06) × 10^-2m + (0.92 ±0.32 × 10^-4 m²; for the purely vibrational transition moment, we found ¦R₀₀₀₀^3001_II¦к(0.4351 ± 0.0014)()10^b3 debye; and, for the total band intensity at STP conditions, S_band(30⁰1_II←00⁰0)_STP = 1255 ± 9 cm^-1 km^-1 atm^-1.Self-broadening coefficients at 197 and 294 K were also measured, as well as broadening by Ar and N₂. Foreign-gas-broadening efficiencies (Ar and N₂) were determined. Finally, a comparison is made with measurements by other authors and with theoretically calculated values.     

High-resolution infrared spectrum of the ν2 + ν3 band of 14N16O2

The ν₂ + ν₃ band of ¹⁴N¹⁶O₂ has been recorded with resolution of 0.028 cm^?1. Ground state and upper state rotational constants have been obtained. The band center obtained, ν₀ = 2355.1517 ± 0.0011 cm^?1 (error cited is 3σ), has been combined with the band centers recently determined for ν₃ and ν₂ to calculate X₂₃ = ?11.348 ± 0.020 cm^?1 where the uncertainty cited is based on reasonable estimates of the absolute frequency error.     

Cross sections for slow ion production and charge transfer in H+3(D+3)−H2(D2) collisions

Slow ion production cross sections for collisions of H⁺₃ and D⁺₃ ions with H₂ and D₂ have been measured at collision energies between 100 eV and 500 eV. The values vary from 2 × 10^-17 cm² to 6 × 10^-17 cm². The smaller cross sections for D₃ projectiles may be explained as an internal energy effect.     

Energy band structure and modulation spectra of A2B4C25 semiconductors

The results of the energy band structure calculations of A²B⁴C₂⁵ compounds are reviewed, and the differences in the energy spectra passing from A³B⁵ semiconductors to their closest ternary analogs are described. The origin of the lowest conduction band minima of A²B⁴C₂⁵ compounds was determined from the slopes of the fundamental absorption edge and the pressure coefficients of the energy gap. The investigations of the valence band structure from electroreflectance (ER), thermoreflectance (TR) and wavelength modulated absorption (WMA) spectra are reviewed. In the higher energy region the ER and TR spectra of A²B⁴C₂⁵ compounds were found to be more complicated in comparison with those of their binary analogs. A model of an assignment of the structures in optical spectra of A²B⁴C₂⁵ compounds is discussed.