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.     

Intensity measurements for the (2, 0) γ-band of O2, b1Σ+g−X3Σ-g

Quantitative intensity measurements have been made for the oxygen γ-band at 6280 Å. Intensities for 19 individual rotational lines of the P_P and P_Q branches and the intensity of the combined R_R and R_Q branches are reported. The band intensity, S^v′_v^″, is found to be 1.52±0.07 cm^-1km^-1atm^-1 (STP).     

Observation of the c3Πu-X1Σg+ intersystem transition in the absorption spectrum of P2

The observation of the c³Π_u-X¹Σ_g⁺ intersystem transition of P₂ is reported. The 6-0 band of the system was identified on high resolution absorption plates teken on the NRC 10-m vacuum spectrograph at Ottawa. A rotational analysis of the band is given together with that of the adjacent 5-0 band of the C¹Σ_u⁺-X¹Σ_g⁺ system, the upper level of which is involved in a mutual perturbation with the c³Π_u, v = 6 level. The interaction parameters for the perturbation are derived. It is proposed that the appearance of the 6-0 band of the c³Π_u-X¹Σ_g⁺ transition is due to intensity borrowing from the strong, allowed C¹Σ_u⁺-X¹Σ_g⁺ system. Accurate values for the energies of the c³Π_u, b³Π_g, and a³Σ_u⁺ states relative to the ground state are given. The analysis of two other bands, 2-0 and 7-0, of the C¹Σ_u⁺-X¹Σ_g⁺ system whose upper levels likewise interact strongly with the c³Π_u state are also given.     

Selenium dioxide: Vibrational analysis of the 3130 Å1B2-X̃1A1 absorption system

The B absorption system of the three isotopic species ⁷⁸Se¹⁶O₂, ⁸⁰Se¹⁶O₂, and ⁷⁸Se¹⁸O₂ have been comparatively studied in the vapor phase. The 0_0⁰ band is at 31955.0/31957.4/31963.9 cm^?1, respectively. The main vibrational structure is due to 1_0ⁿ2_0^m progressions, with maximum intensity at n ～ 6. The stronger progressions are those with m = 0, 1, 2, 3. The progressions are severely perturbed. The molecule is bent in both of the combining electronic states. In the ground state for the (80, 16) species, ν₁″(a₁) = 922.6, ν₂″(a₁) = 372 cm^?1. In the electronically excited state, identified as ¹B₂, ν₁′, and ν₂′ have the approximate values 649 and 258 cm^?1, respectively. Evidence is presented in favor of a double-minimum potential function with respect to Q₃′, the band 3_0¹ being observed with appreciable intensity. The height of the potential barrier is about 600 cm^?1.     

Fluorescence from the 2B1 state of NO2 excited at 4545 Å

The 4545 Å line of the Ar⁺ laser has been used to excite a ^pR₁ line of a vibrational band of the ²B₁-²A₁ system of nitrogen dioxide. Fluorescence from the upper level to the ground electronic state forms a long progression in the bending vibration. This progression can be followed from v″₂ = 0 up to v″₂ = 12, and the fluorescence intensity passes through several local minima as a function of v″₂. The main features of the intensity distribution can be reproduced using a model Hamiltonian which separates the bending and rotation from the stretching vibrations. This Hamiltonian can also be used to reproduce the fluorescence frequencies by adjusting the potential function of the lower state.     

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.     

Extended assignment and analysis of the ν2 and ν4 infrared bands of 12CH4

Infrared spectra of the ν₂ and ν₄ bands of ¹²CH₄ have been assigned up to J′ = 20 in the ν₄ band and J′ = 17 in the ν₂ band. Assignments are presented for over 1000 transitions ranging from 1123 to 1712 cm^?1, which involve 652 upper-state energy levels of the two bands. The 652 upper-state levels have been fitted with a weighted standard deviation of 0.0026 cm^?1, almost all levels being reproduced to within their experimental error, by a Hamiltonian for the coupled upper states containing 28 refining parameters and 4 fixed parameters. Calculated relative intensities are also tabulated and discussed in relation to recent experimental intensity measurements.     

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.     

Absorption of monodeuteromethane 12CH3D at 4.5 μM,analysis of the overtone band 2ν6

The overtone band 2ν₆ of ¹²CH₃D is analyzed in the range 2088–2433 cm^?1. The parallel and perpendicular components, centered at 2316.266 and 2323.297 cm^?1, are strongly interacting, giving rise to a number of “forbidden” transitions and large A₁A₂ splittings. Six hundred twelve transitions including J′ values up to 13 are assigned; the vibration-rotation constants for the upper state v₆ = 2 are derived from these data, allowing the reproduction of the experimental wavenumbers with a rms equal to 0.007 cm^?1. Some intensity measurements are used to estimate the overall band strength of 2ν₆.     

New infrared integrated band intensities for HC3N and extensive line list for the ν5 and ν6 bending modes

The infrared spectrum of cyanoacetylene (also called propynenitrile) has been investigated from 400 to 4000 cm⁻¹ at a resolution of 0.5 cm⁻¹. Integrated intensities of the main bands and a number of weaker bands have been obtained with an uncertainty better than 5%. Inaccurate values in previous studies have been identified in particular concerning the intensity of the strong ν₅ stretching band at 663.2 cm⁻¹. Former results on the temperature dependence of integrated intensities have also been revisited.Synthetic spectra calculation has been performed for the ν₅ and ν₆ bands on the basis of the best available high resolution data. It has been shown that the GEISA line parameters for HC₃N are not sufficient to reproduce the band intensities and some hot band features observed in our experimental spectra at room temperature. As a first step, the model spectra has been improved by including a number of missing hot subbands and by calculating accurately the hot band relative intensities. Finally, a perfect agreement between calculated and observed spectra was achieved on the basis of a global analysis of HC₃N levels up to 2000 cm⁻¹ combined with the new integrated intensity measurements. A new extensive line list for the ν₅ and ν₆ bending modes of HC₃N has been compiled.     

Absolute band strengths for the AlO blue-green (B2σ−X2σ) band system

The relative intensity measurements of Linton and Nicholls¹ on the AlO blue-green system have been placed on an absolute scale using the radiative lifetimes of Johnson et al.² and Dagdigian et al.³ for levels of the B²Σ state of AlO. Absolute values of Einstein A coefficients, band strenghts and band oscillator strengths are presented for 75 bands of the system.     

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.     

X-ray spectroscopic study of the valence band structure of Cd1−xMnxTe, x = 0.6

The valence band structure of Cd_1?xMn_xTe (x = 0.6) was studied by soft X-ray emission spectroscopy using a 11.5 m concave grating grazing incidence spectrometer in conjunction with a high power rotating anode, which provided the radiation for flourescence excitation. The position of the Mn 3d⁵ states within the energy band system could be identified unambiguously; they form a band near the top of the CdTe valence band. The results are discussed with regard to recently published photoemission data.     

Vibrational analysis of the a3Σ+-X1Σ+ and b3Π-X1Σ+ band systems of GeS

Spectra of GeS have been obtained in a chemiluminescent flame produced by the reaction Ge + OCS → GeS + CO. Neither of the known band systems, D¹Π-X¹Σ⁺ and E¹Σ⁺-X¹Σ⁺, was observed, but two new band systems in the regions 350–400 and 420–650 nm were obtained. By comparison with similar systems in isovalent molecules, these were assigned as b³Π₁-X¹Σ⁺ and a³Σ⁺-X¹Σ⁺, respectively. Vibrational assignments were made with the help of the germanium isotope effect and vibrational constants were obtained for the states involved. Approximate Morse potential Franck-Condon factors were computed and were shown to fit the general trend of the intensity distribution for both systems. Addition of active nitrogen to the flame was shown to increase the intensity of the b-X system by an order of magnitude while hardly affecting the a-X system. Constants (in cm^?1) obtained for the two new states are: a³Σ⁺: T_e = 21986.3 ± 2.3, ω_e = 388.9 ± 1.0, ω_ex_e = 1.35 ± 0.11; b³Π₁: T_e = 27192.0 ± 1.8, ω_e = 435.4 ± 1.1, ω_ex_e = 1.68 ± 0.20.     

Absolute intensities and pressure broadening coefficients measured at different temperatures for the 201II ← 000 band of 12C16O2 at 4978cm-1

Absolute line intensities and self-broadening coefficients have been measured at 197° and 294°K for the 201_II ← 000 band of ¹²C¹⁶O₂ at about 4978cm^-1. The vibration-rotation factor (F_VR), the purely vibrational transition moment (∣R(O)∣), and the integrated band intensity (S_band) are deduced from the measurements. The results are: F_VR(m)=1+(0.24±0.08)x10^-4m+(0.55+0.21)x10^-4m², ∣R(O)∣= (4.340±0.008x10^-3 debye, S_band=96372±190cm^-1km^-1atm^-1_STP. The results for self-broadening coefficients, as well as for individual vibration-rotation lines, are presented in the text.     

Laser absorption spectroscopy of the A1Σu+-X1Σg+(v′, v″) bands of Na2

Laser absorption spectra of the band system A¹Σ_u⁺-X¹Σ_g⁺(v′,v″) of Na₂ in the range between 16835 and 16960 cm^?1 are analyzed. The spectra are free of first-order-Doppler broadening at low internal temperature. Rotational and vibrational assignments of 10 bands are reported. Rotational and vibrational levels, especially the (22, 1) band, are found to be perturbed by the b³Π_u state. The band origins and line frequencies calculated from previously reported constants do not reproduce the observed values. The disagreement between the calculated and observed values is discussed. More accurate constants are needed to predict the line locations.     

The forbidden far-infrared ν6 band of SF6

The far infrared spectra of SF₆ in the 33-μm region in the gas phase at different pressures and in the liquid phase have been studied. A small band situated at 351 cm^?1 on the high-frequency side of two difference bands situated at 304.5 cm^?1 has been observed in the gas phase. Since the integrated intensity of the 351-cm^?1 band varies linearly with the density, it cannot be collision induced. It appears that it is the forbidden ν₆ band that becomes active by Coriolis interaction. This band is seen in the liquid at about the same frequency when it is deconvoluted from the neighboring broadened and split difference bands.     

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.     

Emission cross sections of the second positive and first negative systems of N2 and N+2 excited by electron impact

Cross sections have been measured for emission of the 2nd positive system of N₂ and the 1st negative system of N⁺₂ by electron excitation. The electron energy ranged from the threshold to 400 eV. To obtain absolute values, comparison with the emission cross section of the 5¹S He level has been used.The results for the (0, 2) band of the 2nd positive system and for the (0, 1) band of the 1st negative system are (2.87 ± 0.40) × 10^-18 and (5.35 ± 0.5) × 10^-18cm², respectively, at the peak. The cross sections are given for 23 bands of the 1st negative systems.Use of the (0, 1) band of the 1st negative system is proposed for reference in obtaining absolute values.