High precision spectrum of N2O at 4.5 μm and determination of molecular constants for the ν3 and the (ν2 + ν3 − ν2) bands

A high precision wavenumber calibration has been achieved for the spectrum of N₂O at 4.5 μm. The values of the wavenumbers are reported for the (00°1-00°0) and for the (01¹1-01¹0) transitions. A new set of molecular constants is given for the upper and lower levels of these two transitions. In particular, the value of the H constant for the ground state (?2.02 ± 0.4) × 10^?13 cm^?1 determined in this work is significantly different from previous results.     

Line strengths and self-broadened linewidths of N2O in the 2-μm region: 2400-0000 and 0112-0000 transitions

The strenghths and self-broadened linewidths of the parallel 24⁰0-00⁰0 and perpendicular 01¹2-00⁰0 bands of N₂O have been measured with a precision better than 3%, using a deconvolution procedure. For both transitions, the coefficient of the vibration-rotation interaction polynomial, the values of the rotationless dipolar transition moment, and the band intensity have been calculated from the line strengths. For the total intensity the values found are S_00⁰0²⁴⁰⁰ = (1.325 ± 0.021) × 10^?2 cm^?2·atm^?1 and S_00⁰0⁰¹¹² = (1.209 ± 0.018) × 10^?2 cm^?2·atm^?1.     

Line intensities of CO2 in the 2·7 micron region

Individual line intensities have been measured at 0·025 cm^?1 resolution and low pressures for the two strong Σ-Σ bands of C¹²O₂¹⁶ near 2.7 microns, as well as for their associated Π-Π hot-bands. Values of the rotationless dipole-moment matrix elements and vibration-rotation interaction coefficients are reported along with total band intensities. Results for the latter in cm^?2 atm^?1 at 296°K are: 25·7, 1·96, 39·3 and 3·23 for the 02⁰1-00⁰0, 03¹1-01¹0, 10⁰1-00⁰0, and 11¹1-01¹0 bands, respectively.     

Infrared spectra of CS2: Measurement of “hot” bands associated with the 2325 cm−1 and 2962 cm−1 bands

The 12⁰1-00⁰0 and 02⁰1-00⁰0 transitions of CS₂ have been measured with a resolution of 0.025 cm^?1. The following “hot” bands associated with these transitions were also measured 13¹1?01¹0, 22⁰1? 10⁰0, 14⁰1?02⁰0, 14²1?02²0, 03¹1?01¹0, 12⁰1?10⁰0, 04⁰1?02⁰0, 04²1?02²0, 13¹1?11¹0, and 22⁰1?20⁰0. Improved rotational constants are given for the ground state and the first bending state. A consistent set of band constants is given for all the above vibrational transitions.     

Intensity of CO2 bands in the 4.8- to 5.3-μm region. The (1110,0310)II-0000 band

Measurements of the line strengths of the (11¹0,03¹0)_II-00⁰0 band of CO₂ (1932.466 cm^?1) have been made with high resolution. They exhibit a strong Coriolis interaction which enhances the P-branch intensity while reducing that of the R branch. The rotationless dipole moment of the transition and the ξ-constant representing this interaction have been determined as: R(0) = (6.57 ± 0.03) × 10^?4D, ξ = ?0.0598 ± 0.0002.     

High-resolution infrared spectrum of the 859- and 1711-cm−1 bands of carbonyl sulfide (OCS)

The ν₁ and 2ν₁ bands of OCS have been measured using grating spectrometers and a tunable diode laser spectrometer. Preliminary wavenumbers for OCS absorption lines useful for calibrating tunable laser systems are given for the wavenumber intervals 825 to 885 cm^?1 and 1665 to 1737 cm^?1. Measurements and an analysis are given for the bands 10⁰0-00⁰0, 11¹0-01¹0, 20⁰0-00⁰0, 21¹0-01¹0, and 30⁰0-10⁰0 of the ¹⁶O¹²C³²S isotopic species and for the 20⁰0-00⁰0 band of the ¹⁶O¹³C³²S and ¹⁶O¹²C³⁴S species. Effective band constants are given for these bands.     

Heterodyne frequency measurements on N2O near 1060 cm−1

The results of heterodyne frequency measurements are given for the 10⁰0-02⁰0 band of N₂O centered at 1056 cm⁻¹. Nine lines are measured and fit with an rms deviation of 1.3 MHz. The data are combined with other infrared and microwave data in a least-squares fit that gives accurate ro-vibrational constants for the two states involved in these transitions. The analysis of the data is based on a treatment that includes the effect of l-type resonance between the 02⁰0 and 02²0 states. Derived tables of wavenumbers are given for the 02⁰0-00⁰0 band near 1168 cm⁻¹ and the 02⁰1-00⁰0 band near 2460 cm⁻¹.     

High resolution infrared spectrum of 13CS2 between 250 and 430 cm−1

The high resolution infrared spectrum of ¹³CS₂ between 250 and 430 cm^?1 has been studied with a Fourier transform spectrometer at a resolution of about 0.010 cm^?1. The following bands are analyzed: the bending fundamental 01¹0←00⁰0 of ¹³C³²S₂ and the associated “hot” bands 02²0←01¹0, 02⁰0←01¹0, 03³0←02²0, 03¹0←02⁰0, 03¹0←02²0, 11¹0←10⁰0, the difference band 10⁰0←01¹0 of ¹³C³²S₂, and the bending fundamental 01¹0←00⁰0 of ³²S¹³C³⁴S. The polynomial fits were used in the analyses. The rotational constants B and D together with the vibrational term values have been derived for the states involved. The l-type doubling constant q has been obtained for the Π-states 01¹0, 11¹0, and 03¹0 of ¹³C³²S₂.     

Theoretical integrated intensities for the 2ν2 and 2ν2-ν2 bands of HCN and DCN

Dipole moment functions, both perpendicular and parallel to the molecular axis, are calculated from the SCF and MRD-CI results of a previous study for the normal ν₂ bending vibrations of HCN and DCN. Vibrationally averaged dipole moments and the infrared transition matrix elements are then obtained from the dipole moment functions and vibrational wave functions. MRD-CI results, with known experimental values in parentheses, for HCN are 〈0|μ|0〉 = ?2.954(?2.985) D, 〈1|μ|1〉 = ?2.915(±2.942) D, 〈0|μ|1〉 = 0.148(0.147) D, 〈0|μ|2〉 = ?0.027 D, 〈1|μ|2〉 = 0.210 D. Calculated absolute intensities at 1 atm and 0°C for the (02⁰0) ← (000), (02⁰0) ← (010), and (02²0) ← (010) bands of HCN are 25 (40 ± 10 as estimated from spectra), 8.5, and 17.0 atm^?1 cm^?2, respectively. Results for DCN are also reported.     

Laser Stark spectroscopy of OCS in the 9.5 μm region

Laser Stark spectra of carbonyl sulfide have been measured with parallel and perpendicular polarization of a 9.4 μm band CO₂ laser with the Stark field up to 90 kV/cm. Components of the P(2) and R(1) transitions of the 03¹0–01¹0 band and those of the P(1) transition of the 04⁰0–02⁰0 band for ¹⁶O¹²C³²S have been analyzed. Band origins, 1052.9446 (4) cm^?1 for 03¹0–01¹0 and 1057.7860 (5) cm^?1 for 04⁰0–02⁰0, and dipole moments, 0.7035 (16) D for 01¹0 and 0.6810 (24) D for 03¹P, are obtained.     

A study of the fundamental and first overtone bands of NO in NO-rare gas mixtures at pressures up to 10,000 PSI

The absorption intensities of the 1-0 and 2-0 vibration-rotation bands of NO are determined from the absorption coefficients of NOHe and NOAr gaseous mixtures at high pressures at room temperature. The values obtained are: A_1-0 = 121 ± 6 cm^?2 Agt^?1 and A_2-0 = 2.17 ± 0.11 cm^?2 Agt^?1. A theory developed by Tipping is applied to evaluate the dipole moment coefficients unambiguously, including their signs, from the absolute intensity values and the difference between the mean frequency factor and the band origin. The following expansion for the dipole moment function in the ground state of NO is determined: M(x) = ?0.166 + 2.54x ? 1.99x² (in Debye). The absorption profiles of both the 1-0 and 2-0 bands in NOAr mixtures show marked changes as gas pressure increases; some of the factors influencing the shapes of the bands are also discussed. The plots of the integrated intensity vs rare gas density are found to be straight lines with positive slopes. This linear increase of the band intensity with density is interpreted as mainly due to the apparent induced absorption.     

Laser Stark spectroscopy of DCN and DC15N

Using a CO laser, laser Stark resonance spectra were measured for the CN stretching fundamentals (the 00⁰1-00⁰0 bands) of D¹²C¹⁴N and D¹²C¹⁵N near 1925 cm^?1. Laser Stark resonances were also measured for the hot band 01¹1-01¹0 of D¹²C¹⁴N. In addition to accurately determining the band centers, dipole moments are given for the different vibrational states involved.     

Laser microwave double resonance spectroscopy of OCS with a 9.4-μm CO2 laser: Precise measurement of dipole moment in the 0310 vibrational state

A CO₂ laser microwave double resonance experiment in the presence of an intense Stark field was applied to the 01¹0 and 03¹0 vibrational states of the OCS molecule. The precise dipole moment of the 03¹0 state, 0.68173 ± 0.00020 D, was determined. The 03¹0←01¹0 band origin was obtained as 1052.94429 ± 0.00020 cm^?1. This technique is very useful for accurate calibration of the space between Stark electrodes.     

Rotational analysis of the B-X band system of the SbO molecule

Rotational analyses of the two 0-0 bands of theB ²ΣX ²Π_reg system of SbO were carried out for the first time from spectrograms taken in the second order of a 21 ft. concave grating spectrograph having a dispersion of 1·25 Å/mm. The rotational constants of the ν=0 vibrational levels of the upper and lower states, and of the coupling constant A₀ of the lower²Π_reg state were deduced. These values are summarised below. v₀₀=25 334·93 cm^?1 B′₀=0·3190 cm^?1 B″₀=0·3490 cm^?1 A ₀=2276 cm^?1 r′₀=1·933 Å r″₀=1·848 Å.     

The forbidden (J → J + 1) spectrum of CH4 in the ground vibronic state

The pure rotational R-branch spectrum of CH₄ arising from the centrifugal distortion moment has been studied using a simple 12.10-m light-pipe cell and a conventional interferometer. Ten forbidden (J → J + 1) transitions for J = 7 to J = 16 have been observed in the spectral region 80–200 cm^?1 with a theoretical resolution of 0.5 cm^?1. The integrated intensity of the six strongest lines has been measured and was found to be of the order of twice that calculated from the distortion moment obtained earlier from a molecular beam study of the (J = 2) rotational level. In the approximation that frequency shifts due to this excess intensity are neglible, it has been determined that the rotational constant B₀ = (5.245 ± 0.004) cm^?1 and the scalar distortion constant D_S = (1.19 ± 0.09) × 10^?4 cm^?1. It is argued that the excess intensity is due to higher-order terms in the dipole moment operator and the validity of the frequency analysis is considered in this context.     

Heterodyne frequency measurements on N2O between 1257 and 1340 cm−1

Frequency measurements are given for the 00⁰1-00⁰0 and 01¹1-01¹0 bands of N₂O from 1257 to 1340 cm^?1. The measurements utilize heterodyne techniques by measuring small frequency differences between a tunable diode laser locked to the center of an N₂O absorption line and harmonic combinations of frequencies of radiation from two CO₂ Lamb-dip-stabilized lasers. The measurements are facilitated by the use of the CO laser as a transfer laser whose frequency is also measured. These measurements have been combined with other data to provide new band constants and frequency calibration tables for several band systems of N₂O in the following regions; 1215 to 1340, 1816 to 1930, and 2135 to 2268 cm^?1. A correction factor is also provided for existing calibration tables near 590 cm^?1.     

The ν4 and ν2 Raman bands of CHD3

The CHD₃ Raman spectrum from 1925 to 2455 cm^?1 has been photographed with a resolution of about 0.2 cm^?1, showing the overlapping ν₂ and ν₄ bands. Ground state combination differences yield C₀ = 2.6297 ± 0.0003 cm^?1. The ν₄ state is weakly perturbed, but reasonably accurate values could be obtained for ν₄ = 2250.88 ± 0.10 cm^?1, (Cζ)₄ = 0.656 ± 0.010 cm^?1, C₄ - C₀ and B₄ - B₀. Some of these constants differ significantly from values previously estimated by infrared workers. For the ν₂ state the constants determined are in good agreement with recent infrared results.     

Strong selective excitation of Raman-active vibrations and energy transfer between low-lying vibrational states of a CO2 molecule studied by PARS and CARS

We experimentally demonstrate the novel technique of inducing the highly nonequilibrium distribution of molecules over vibrational states by two-frequency coherent Raman excitation. The technique can be used for selective excitation of totally symmetric and other Raman-active molecular transitions. Two counter propagating focused laser beams (second harmonic of Nd: YAG and dye laser) were used to induce population difference changes at the 00⁰0–10⁰0 transition in CO₂ molecules. The excitation and relaxation kinetics of this and neighbours vibrational modes of CO₂ were studied both by CARS and PARS. Vibrational excitation of up to 20% of the total number of irradiated molecules is measured; previously unknown desactivation constant of CO₂ (10⁰0) and CO₂ (02⁰0) states via CO₂ (01¹0) state is estimated to be K = (3±1) × 1 ⁵s^-1torr^-1.     

Microwave spectroscopy of OCS in highly excited vibrational states through energy transfer from N2

The efficient vibrational energy transfer between the first excited vibrational state of N₂ and the asymmetric stretching vibrational state of OCS has allowed the observation of many pure rotational lines in different vibrational states of OCS up to 4101 cm^?1: (00⁰1), (01¹1), (02^l1), (10⁰1), (00⁰2), (21¹0), (03^l0), (04^l0), and (05^l0). Accurate values of some rotational, centrifugal distortion and l-doubling constants are determined.     

Absolute OCS wavenumbers and analysis of bands in the region of the lowest fundamental ν2

The high-resolution infrared spectrum of carbonyl sulfide (OCS) in the region 490–560 cm^?1 has been recorded with a Fourier transform spectrometer at a resolution of about 0.005 cm^?1. Measurements and analysis are given for the bands 01¹0 ← 00⁰0, 02²0 ← 01¹0, and 02⁰0 ← 01¹0 of the ¹⁶O¹²C³²S isotopic species and for 01¹0 ← 00⁰0 of the ¹⁶O¹²C³⁴S species.