Laser Stark spectroscopy of thioformaldehyde in the 10-μm region: The ν3, ν4, and the ν6 fundamentals

The ν₃, ν₄, and ν₆ bands of thioformaldehyde, H₂CS, have been studied using the technique of laser Stark spectroscopy. The H₂CS was produced by the pyrolysis of dimethyl disulfide, and the spectrum was observed using a multipass absorption cell. The band origins are ν₃, 1059.2037 cm^?1; ν₄, 990.1866 cm^?1; and ν₆, 991.0149 cm^?1. The band previously assigned as 2ν₆ has been reassigned as 2ν₂, leading to a value of the ν₂ band origin of ca. 1439 cm^?1. Rotational constants and dipole moments of the vibrational states have been determined.     

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.     

Wavenumbers,line strengths,and assignments in the Doppler-limited spectrum of formaldehyde from 2700 to 3000 cm−1

The spectrum of H₂CO from 2700 to 3000 cm^?1 has been examined at Doppler-limited resolution using a tunable difference frequency laser spectrometer at Lincoln Laboratory. The wavenumbers and strengths of 4350 absorptions have been determined with an accuracy of 0.001 cm^?1 and 5%, respectively. These data have been incorporated into the analysis of lower-resolution data from Florida State University to assign 72% of the observed absorptions to one of seven bands: ν₃ +ν₄ (a C-type band at 2655 cm^?1), ν₃ + ν₆ (a B-type band at 2719.156 cm^?1), ν₁ (an A-type band at 2782.457 cm^?1), ν₅ (a B-type band at 2843.326 cm^?1), ν₂ + ν₄ (a C-type band at 2905 cm^?1), 2ν₃ (an A-type band at 2999.5 cm^?1) and ν₂ + ν₆ (a B-type band at 3000.066 cm^?1). The band ν₃ + ν₄ has been observed for the first time, and the band center for 2ν₃ has been corrected from a value of 2972 cm^?1 to the value listed above. The effects of strong Fermi and Coriolis resonances on the spectra are discussed.     

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.     

Study of the ν2 + ν3 and 2ν6 infrared bands of CH379Br and CH381Br

The rotational analysis of the ν₂ + ν₃ band, centered around 1912 cm^?1, and of both components 2ν₆^±2 and 2ν₆⁰, centered about 1912 and 1904 cm^?1, respectively, has been carried out from a Fourier transform spectrum having a resolution limit of 0.005 cm^?1. A standard deviation of about 0.001 cm^?1 was obtained for about 750 lines of the unperturbed 2ν₆^±2 component for both isotopic species. The ν₂ + ν₃ band, stronger than 2ν₆^±2, is perturbed by two resonances: a Coriolis resonance with the very weak ν₃ + ν₅ band, no line of which has been observed, and an anharmonic resonance with 2ν₆⁰, only four K subbands of which have been observed. For both isotopic species, a standard deviation of about 0.002 cm^?1 has been obtained for about 750 lines of ν₂ + ν₃ and 2ν₆⁰.     

A High-Resolution Analysis of the ν3 Absorption Band of Trifluoromethane

A high-resolution (up to 0.0018 cm⁻¹ unapodized) room temperature mid-infrared (650 to 750 cm⁻¹, 13.3 to 15.4 μm) absorption measurement of the ν₃ vibrational band of trifluoromethane (fluoroform, CHF₃, HFC-23) vapor was made with a Fourier transform spectrometer. A rovibrational analysis of over 1400 infrared transitions of the ν₃ band has yielded rotational constants, including sextic centrifugal distortion constants. The results are compared with two previous analyses of microwave and infrared spectra. The line positions of the lower J parts of the ν₃+ν₆−ν₆ and 2ν₃−ν₃ hot bands have been identified and constants obtained for the 2ν₃ state. The central Q branch and a few unblended transitions of the ν₃ band of ¹³CF₃H have been identified and the band origin has been determined. The relative intensities of the ν₃ band together with the 2ν₃−ν₃ hot band and ν₃ band of ¹³CF₃H have been calculated using the constants derived from this work.     

Extensive high-resolution study of the crowded rovibrational CH3F spectrum around 3000 cm−1

The infrared spectrum of CH₃F has been remeasured from 2800 to 3160 cm^?1 with a Fourier spectrometer at a resolution of 0.005 cm^?1. By a systematic use of ground-state combination differences, we have assigned 5200 transitions, including several hundred “forbidden” transitions. They can be distributed into seven vibrational bands, which are mixtures of ν₄, ν₁, 2ν₅², 2ν₅⁰, ν₂ + ν₅, 2ν₂, and 3ν₃. More than 20 local resonances have been detected as well as 11 subbands with A₁A₂ splittings. We have attempted to fit all these data in a global model of the “limited-matrix” type including the 6 × 6 resonance due to ζ₂₅^ν, two Fermitype resonances linking ν₁ with 2ν₅⁰ and 2ν₂, respectively, a Coriolis resonance between ν₄ and 2ν₅², and other minor interactions. We conclude that the use of an “infinite-chain” program is unavoidable. We have also identified 80 transitions as belonging to the ν₄ band of ¹³CH₃F occurring in natural abundance.     

Infrared spectra of 1-phosphapropyne,CH3CP,and its perdeuteride,CD3CP

The infrared spectra of 1-phosphapropyne, CH₃CP, and its perdeuteride, CD₃CP, have been measured in the gaseous and solid states. The Q_K branches of perpendicular bands have been analyzed in terms of the usual quadratic expression in K. Fermi resonances were identified for the ν₁, ν₂ + ν₃, 2ν₃, 2ν₆⁰; and ν₅, 2ν₃ + ν₈ band systems of CH₃CP and the ν₁, 2ν₃, 2ν₆⁰; ν₆, ν₇ + ν₈; and ν₇, 3ν₈¹ band systems of CD₃CP. The xy Coriolis interaction was also identified between the ν₃ and ν₆ bands of the two species. All the fundamentals were assigned and the normal coordinate treatment was carried out along with the Coriolis constants, ζ^z.     

Subject index for volume 100

The ν₂ fundamental band of HNCO has been observed for the first time under a resolution of 0.015 cm^?1. The band origin for this NCO antisymmetric stretching vibration is found to be at 2268.893 cm^?1, rather distant from the previously reported value of 2274 cm^?1. Nineteen subbands have been analyzed and term values for both ground and ν₂ states with K up to 4 have been obtained. Effective rotational constants B and centrifugal distortion constants D and H have also been determined. Interactions are observed with 2ν₄ + ν₅ and ν₃ + ν₄. Large perturbations are observed for K = 0 and K = 1 levels of ν₂. Transitions are also seen for three other vibrations, ν₄ + ν₅ + ν₆, ν₃ + ν₆, and 2ν₄ + ν₆.     

Absorption strength of the perturbed ν4 band of CH3Cl

The ν₄ band of CH₃Cl interacts strongly with the 3ν₆ band. Levels of both bands are mixed and both appear strongly in absorption. The strengths of both bands have been measured taking into account the mixing of the levels. The absorption strengths of both bands can be related to a single parameter; namely, the strength of the unperturbed ν₄ band. This was calculated to be 41.8 cm^?2 atm^?1 at 297 K.     

High-resolution stimulated Raman gain spectrum of the ν1 band of SF6

We report rotationally resolved stimulated Raman gain spectra of the ν₁ band of SF₆. The fundamental band exhibits a rigid-rotor type spectrum that is readily fit with a band origin of Δα = 774.5445 and a single rotational term Δβ = ?1.10376 × 10^?4 cm^?1. We also observed and analyzed the ν₁ + ν₆ hotband with band origin at 774.1820 cm^?1. With an experimental resolution of 0.0024 cm^?1 there is no evidence for centrifugal distortion or tensor splitting in either band, although the ν₁ + ν₆ band does exhibit first-order Coriolis splitting as expected.     

High-resolution infrared spectrum of CH2D2: The ν3 fundamental band at 7 μm

The infrared spectrum of CH₂D₂ has been recorded in the region of 1345 to 1561 cm^?1 with a resolution of 0.030 to 0.026 cm^?1. Most of the observed lines have been assigned to transitions of the ν₃ band of CH₂D₂. However, 114 lines have been identified as transitions of the ν₂ band of H₂¹⁶O whose band origin has been directly determined to be 1594.7472 ± 0.0030 cm^?1. A few weak lines, probably belonging to the ν₅ fundamental of CH₂D₂, remain unassigned. The band center ν = 1435.1326 ± 0.0030 cm^?1 and a set of upper state constants were obtained for the ν₃ band of CH₂D₂. Although a slight perturbation was noticed in the ν₃ band, all wavenumbers have been fitted with a standard deviation of 3.8 × 10^?3 cm^?1.     

The ν3 band of CD3I around 500 cm−1

The region of the lowest fundamental band ν₃ of CD₃I around 500 cm^?1 is studied at a resolution of 0.015 cm^?1. The K structure in the parallel band ν₃ is resolved for K = 6 – 14. Molecular constants for the ν₃ level are derived, including α₃^A = 3.055(13) × 10^?3 cm^?1. The “hot” band 2ν₃-ν₃ is also investigated.     

Line strengths of the ν3 - ν4 band of methane

Strengths of 413 lines of the ν₃ - ν₄ band of methane from 1568 to 1932 cm^?1 have been measured with 2 to 4% accuracies using spectra recorded at 0.011 cm^?1 (unapodized) resolution. Transition strengths up to J₃ = 14 have been fitted with a standard deviation of 4% using a four-term, first-order expansion of the dipole moment. A band strength of 0.050(2) cm^?2 atm^?1 at 296 K is reported for ν₃ - ν₄ of ¹²CH₄. Estimated band strengths of ν₁ - ν₄, ν₃ - ν₂, ν₃ + ν₄, ν₁ + ν₄, and ν₂ + ν₃ are also given.     

Detection and analysis of new bands of O3 by CRDS between 6500 and 7300 cm

The absorption spectrum of the ¹⁶O₃ isotopologue of ozone has been recorded in the 7000-7920 cm⁻¹ region by high sensitivity CW-Cavity Ring Down Spectroscopy. This report is devoted to the analyses of the 7065-7300 cm⁻¹ region dominated by the ν₁ + 2ν₂ + 5ν₃ and ν₁ + 5ν₂ + 3ν₃ A-type bands at 7130.8 and 7286.8 cm⁻¹ respectively. 289 transitions were assigned to the ν₁ + 2ν₂ + 5ν₃ band. The corresponding line positions were modeled with an effective Hamiltonian involving Coriolis resonance interactions between the (1 2 5) upper state and the (4 4 0), (0 2 6) and (6 1 0) dark states, and an anharmonic resonance interaction with the (2 0 5) state. The very strong interaction (up to 50% mixing of the wavefunctions) between the (1 2 5) and (6 1 0) states leads to the observation of two extra lines of the 6ν₁ + ν₂ band due to a resonance intensity transfer. 213 transitions of the ν₁ + 5ν₂ + 3ν₃ band were assigned and modeled taking into account a Coriolis resonance interaction with the (3 6 0) state.We take the opportunity of the present work to report the analysis of the very weak 4ν₂ + 4ν₃ B-type band at 6506.1 cm⁻¹ which was assigned from previously recorded CRDS spectra. 286 transitions were modeled using the effective Hamiltonian approach.The dipole transition moment parameters of the three analyzed bands were determined by a least-squares fit to the measured line intensities. For the three studied band systems, the effective Hamiltonian and transition moment operator parameters were used to generate line lists provided as Supplementary Materials.     

High-resolution infrared spectrum of the ν1 + ν3 band of ozone

The ν₁ + ν₃ band of ozone (O₃) near 2110 cm^?1 has been measured and analyzed using a Watson-type Hamiltonian including all seven sextic centrifugal distortion terms. Two weak perturbations have been found between K = n of ν₁ + ν₃ and K = n + 3 of 2ν₃. Those perturbations locate the band center for 2ν₃ at about 2058 cm^?1. Aside from those perturbations the interactions of ν₁ + ν₃ with 2ν₁ and 2ν₃ have not been taken into account in the analysis. Effective band constants and an atlas listing line wavenumbers and assignments are given.     

Diode laser measurements of line strengths and widths in the 4.5-μm bands of N2O

We have made line-strength measurements in the N₂O ν₃-fundamental region using a tunable diode-laser spectrometer. From these measurements and the Herman-Wallis factor determined by Boissy et al., we find the ν₃-fundamental band strength to be S_v = 1203 ± 22 cm⁻² atm⁻¹ at 297 K. Line-broadening parameters for two ν₃-fundamental lines were determined using nitrogen (N₂) as the broadening gas. Measured strengths and N₂ line-broadening parameters for several (ν¹₂ + ν₃ − ν¹₂) hot-band lines are also presented.     

Contribution to the study of the 2ν5 (A1) rovibrational band of CH3Br near 2860 cm−1

This band was studied on a Fourier Transform spectrum (resolving power of the apparatus: 0.005 cm^?1). For each isotopic species CH₃⁷⁹Br and CH₃⁸¹Br, about 800 lines were assigned. The band is well explained by a x-y type Coriolis interaction with ν₂ + ν₅. Several local resonances occur for low K values as well as a doubling of the K = 3 levels. Their study provides interesting information on neighboring bands, especially 3ν₆(E), ν₂ + ν₃ + ν₆, and 2ν₅(E).     

The ν4 band of CD3I with perturbations: A high-resolution infrared study

The infrared band ν₄ of CD₃I between 2220 and 2390 cm^?1 has been investigated at a resolution of 5.4 × 10^?3 cm^?1. More than 2000 lines were assigned to subbands with KΔK from ?18 to 21, including J values up to 70. In the analysis the Coriolis resonances with ν₃ + ν₅^±1 + ν₆^±1, ν₂ + 2ν₆^±2, ν₂ + 2ν₆⁰, and 2ν₃ + 2ν₆^±2 were taken into account. The molecular constants concerning the fundamental ν₄, as well as the parameters describing the combination levels, were derived.     

Subnanosecond transient photocurrents in a-Si:H: A probe of thermalization within shallow band-tail states

The measurement of transient photocurrents in amorphous semiconductors has been shown to be a powerful way of exploring the thermalization of excess carriers within the manifold of localized states adjacent to the band edges. The extent to which thermalization within the shallowest states can be resolved in controlled by the experimental observation time. Reported here are measurements of transient photocurrents, using high-speed stripline techniques, in glow-discharge a-Si:H carried out in the time regime (0.6 ? 100 nsec) and the temperature range 150 ? 320K. We find an effective electron drift mobility of <μ_D(t)> = 1–3 cm²/Vsec at t=0.6 nsec and T=300K and a time-dependent activation energy, _?(t), for the photocurrent magnitude. The initial photocurrent decay (t < 100 nsec) can be fit to a power-law, t^?n, and the temperature dependence of the dispersion parameter, α=1?n, is given by α=α₀+βT. In view of these results the nature of the band-tail near the conduction band edge is discussed.