Collisional transfer between rotational levels of OCS

Steady-state four-level microwave double-resonance experiments are described for pure OCS and OCS diluted with CH₃OH, H₂, and He. For pure OCS, interactions of higher order than first-order dipole-dipole dominate the behavior of some four-level systems, and the rates of ΔJ = 2 quadrupole-type collision-induced transitions are found to be greater than one-half of the ΔJ = 1 dipolar rates. For OCSCH₃OH mixtures, the dipolar rates are significantly enhanced with respect to the pure gas, but ΔJ = 2 transitions are still important. For the mixtures of astrophysical interest, OCSH₂ and OCSHe, all four-level systems show ΔJ = 2 collisional preferences. The ΔJ = 2 transition rates are comparable to those of ΔJ = 1 transitions, and there is evidence that ΔJ = 3 transition rates are substantial.     

The microwave spectrum and structure of chloromethyl cyclopropane

The microwave spectra of $\text{CH}{}_2\text{CH}{}_2\text{CH}$CH₂³⁵Cl and $\text{CH}{}_2\text{CH}{}_2\text{CH}$CH₂³⁷Cl have been observed and lines assigned to the gauche form. The rotational constants in MHz and distortion constants in KHz are: C₃H₅CH₂³⁵Cl, A = 11745.65, B = 2047.274, C = 1886.622, Δ_J = 0.85, Δ_JK = ? 0.9, Δ_K = 44., δ_J = ? 0.099, δ_K = 19.1, C₃H₅CH₂³⁷Cl, A = 11691.61B = 1997.664, C = 1842.823, Δ_J = 0.7, Δ_JK = ? 64.6, Δ_K = 2400, δ_J = 0.19, δ_K = ? 67.     

Diode laser spectra of the ν2 band of H212CO and H213CO

The Q-branches of the ν₂ (CO stretch) band of H₂¹²CO and H₂¹³CO have been studied in high resolution using an infrared diode laser. Accurate upper state constants, including A, B, C, Δ_J, Δ_JK, Δ_K, and H_K, were determined from an analysis of the data for 97 lines of H₂¹²CO and 79 lines and H₂¹³CO and compared with previous reported values. Band centers were also determined and reported as 1746.009 ± 0.002 cm^?1 for H₂¹²CO and 1707.981 ± 0.002 cm^?1 for H₂¹³CO.     

ΔK = 2 transitions in H2CO and D2CO

Weak transitions of the type ΔJ = ± 1, $\text{Δ}\text{K}{}_{\mathrm{a}}\text{= ? 2}$, ΔK_c = ± 3 have been observed in H₂CO and D₂CO by the millimeterwave double resonance method and also by direct absorption with a Stark modulated spectrometer. The addition of these new transitions in a least-squares analysis, in which all previously known microwave and millimeterwave data are also included, results in an improved set of rotational and distortion constants.     

M-dependence of collisional transfer of rotational energy in OCS mixtures

Collision-induced transitions between rotational levels of OCS in the ground vibrational state have been investigated by steady-state microwave double resonance, with the M sublevels separated by a Stark field. The (2 ← 1)_P-(1 ← 0)_S, (3 ← 2)_P-(1 ← 0)_S, and (4 ← 3)_P-(1 ← 0)_S systems have been studied for pure OCS and for mixtures with excess CH₃OH, He, and H₂. For four-level systems having dipolar connections (ΔJ = 1; ΔM = 0, ± 1; parity ± ? ?) between pump and signal levels, it is found for OCS and the OCS-CH₃OH mixture that the dipole-type ΔJ = 1 transitions always dominate the collisional transfer, but for the OCS-He and OCS-H₂ mixtures that ΔJ = 2 quadrupole-type transitions are dominant. For all four collision partners, significant ΔJ = 2 and ΔJ = 3 collisional transfer is observed in some systems, indicating the presence of high-order terms in the collisional interaction.     

The microwave spectra and structures of epihalohydrins: Epichlorohydrin

The microwave spectrum of the two chlorine isotopic species of epichlorohydrin ($\text{CH}{}_2\text{OCH}$CH₂Cl) is reported. The structure is a gauche conformation with the Cl atom twisted toward the oxygen side of the ring. The observed rotational constants (in MHz) and centrifugal distortion constants (in kHz) are: C₂H₃OCH₂³⁵Cl; A = 13 373.02, B = 2080.353, C = 1932.469, Δ_JK = ? 6, Δ_K = 2400, δ_J = ? 0.43, δ_K = 17, H_KJ = ? 0.13, H_K = 570, h_JK = 0.061, h_K = ? 5.1: C₂H₃OCH₂³⁷Cl; A = 13 361.24, B = 2028.853, C = 1887.990, Δ_JK = 0.31, Δ_K = 1669., δ_J = ? 0.16, δ_K = 54.1.     

Deexcitation of Cd 53P1 atoms in collisions with ground state atoms and molecules

Collisions of excited Cd 5³P₁ atoms were investigated using atomic fluorescence spectroscopy. Cadmium vapor, together with a quenching gas, was irradiated in a quartz fluorescence vessel with Cd 3261 Å resonance radiation and the intensity of the resulting resonance fluorescence was monitored in relation to the gas pressures. The experiments yielded the following cross sections Q₁₀ (in A²) for collisional transfer 5³P₁→5³P₀: CdAr=2×10^?3, CdN₂=8.0, CdH₂=7.0, CdCO=15.6. The cross sections Q for collisional deexcitation to the ground state (quenching) in A² are CdN₂ = 2.6×10^?2, CdH₂ = 11.0, CdCO = 3.4, CdCO₂ = 26.     

Microwave spectrum,centrifugal distortion,substitution structure,and dipole moment of sulfine,CH2SO

The microwave spectrum of the reactive species sulfine (CH₂SO) has been studied. Assignments of 86 transitions of the ground vibrational state normal isotopic species, with J up to 60, have allowed a thorough centrifugal distortion analysis. With planarity implied by the I_c-I_a-I_b value of 0.1333 amu $\text{A}\text{?}{}^2$, spectral assignments of seven other isotopic modifications have resulted in the following substitution bond lengths and angles: CH_syn = 1.085 Å, CH_anti = 1.077 Å, CS = 1.610 Å, SO = 1.469 Å, ?HCH = 121.86^°, ?SCH_syn = 122.51^°, ?SCH_anti = 115.63^°, and ?CSO = 122.51^°. From Stark effect measurements of the normal and d₂ species, the dipole moment has been determined to be 2.994 D, oriented 25.50° relative to the SO bond and 9.61° relative to the normal species “a” axis. At an initial pressure of 30 mTorr in a clean brass waveguide, the lifetime of sulfine at 25°C is ～30 min.     

Pressure-induced H2 opacity in the 5-μm region

The H₂ opacity arising from the pure-rotational hexadecapole-induced U₀(J) transitions occurring during H₂H₂ and H₂He collisions, and from the hexadecapole-induced U₀(J) + S₀(J′) and the quadrupole-induced S₀(J) + S₀(J′) transitions in H₂He collisions, has been calculated. The U₀(J) and S₀(J) + S₀(J′) contributions from H₂H₂ collisions are important H₂ opacities in the frequency range from 700–3000 cm^?1 for temperatures appropriate to the outer planets. It is concluded that this opacity is needed in addition to the opacity from the extrapolation of the 0-0 and 1-0 H₂H₂ collisionally induced bands to interpret the spectrum at 5 μm for the outer planets.     

Helium and self-broadening in the first and second overtone bands of 12C16O

The pressure broadening coefficients for rotation-vibration lines of J states up to 22 in the 2-0 band and J states up to 20 in the 3-0 band of pure CO and HeCO mixtures were measured. The data were obtained at room temperature utilizing a Fourier transform spectrometer and various cells, including a 113-m White cell. These data exhibit little change with increasing vibrational level, and in the case of helium broadening, only slight J dependence.     

Low rotational transitions of the CF3H molecule: The pressure-induced shift and broadening

Using a microwave spectrometer with a radioacoustic signal detection, the absorption profiles in the multiplets of the low rotational transitions J’?J = 2?1, 3?2, 4?3, and 5?4 of the ¹²CF₃H molecule in the ground vibrational state at pressures of pure gaseous CF₃H from 0.1 to 1.3 Torr when all the K components of the multiplets merge into a single spectral line are studied. The parameters of the pressure-induced shift and broadening of the observed lines are determined by comparing the theoretically modeled absorption signal and the experimental spectrum. The model used takes into account weak lines corresponding to the excited vibrational states v₃ and v₆ of the ¹³CHF₃ molecule and the instrumental features of the spectrometer. The observed multiplet is simulated as an isolated Lorentzian line and as a sum of the profiles of the K components with known unshifted positions and known amplitude ratio. The shift and broadening parameters obtained in both cases are shown to agree well with each other. The dependences of the shift and broadening parameters on the quantum number J are analyzed and compared with the previously obtained data for the lines J’?J = 1?0 and 2?1.     

The rotational levels of the ground vibrational state of formaldehyde

A variational procedure for rovibrational energy levels and wavefunctions of centrally connected tetra-atomic molecules is extended to include high rotational states, and in particular, J ? 10 levels for the vibrational ground state of formaldehyde. It is very important to do this because it has made possible the calculation of the usual rotational spectroscopic constants which correspond to the forcefield and geometry. A direct comparison with the ‘observed’ spectroscopic constants is therefore possible. The geometry and forcefield are refined against 65 J = 0 levels of H₂CO, 6 J = 0 levels of D₂CO, 42 J = 1, 70 J = 2 and 98 J = 3 levels of the ground and fundamentals of H₂CO and D₂CO, using an iterative scheme. The mean absolute error of the J = 0 levels is 1·10 cm^?1 and that for J ≠ 0 is 0·005 cm^?1, and the predicted geometry is CH = 1·10064 Å, CO = 1·20296 Å and HCO = 121·648°. Finally, the rotational constants A, B, and C for the ground state are 281956, 38846 and 34003 MHz, compared with the observed values 281971, 38836, and 34002 MHz. The centrifugal distortion constants Δ_J , Δ_JK , Δ_K and δ_J , are 77, 1275, 18113 and 11 kHz compared with 75, 1291, 19422 and 10 kHz. These results underline the accuracy of the new quartic forcefield.     

New observations and analyses of the laser excited fluorescence of the A1Σu+-X1Σg+ bands of the Na2 molecule

A medium power (～50 mW, 6328 Å) HeNe laser is used to excite the A¹Σ_u⁺-X¹Σ_g⁺ fluorescence of the Na₂ molecule in a crossed heat pipe oven. The spectrum in the region 5800–8500 Å is recorded both photographically (3.4 M Ebert) and photoelectrically (GaAs detector) with an emphasis on accurate relative intensities and on the observation of higher vibrational levels in the ground state close to the dissociation limit. P and R doublets in four series originating from (v′ = 14, J′ = 45), (v′ = 16, J′ = 17), (v′ = 22, J′ = 86), and (v′ = 25, J′ = 87) levels are observed and identified. The first two series, known from earlier work, are extended further to longer wavelengths to include 13 to 17 additional ground-state vibrational levels. The latter two series are observed for the first time. They originate from higher J′ levels and span a wide range of v″ levels (0 ≤ v″ ≤ 48). Effective RKR potentials for specific J″ (= 17, 45, 86, and 87) quantum numbers of the ground state are constructed and from them the true (rotationless) potential energy curve (for X¹Σ_g⁺) is derived which (a) reproduces the RKR curve previously given by Kusch and Hessel and (b) extends the curve from 5.77 to 7.26 Å (outer turning point). The dissociation energy D_e is estimated from these data to be 6022 ± 21 cm^?1.     

Microwave l-type resonance transitions of the v4 = 1 state in PF3: Detailed interactions and molecular structure

Observation of the direct l-type resonance transitions in the microwave spectrum of the v₄ = 1 state of PF₃ has been extended to J = 36. The w-type interaction, (Δl = 0, ΔK = 6), has been found from measurements on the “forbidden” Stark trasitions in the $\text{K}\text{= 3}$ series. Also in this series a close accidental degeneracy was found between J = 30, $\text{K}\text{= 3}$ and 0, leading to new zero-field “forbidden” transitions through the r-type interaction (Δl = 2, ΔK = ?1) and to the determination of the C rotational constant. Nine spectroscopic parameters were determined using 140 observed frequencies including two “forbidden” trasitions. After suitable correction the B and C constants were used to determine the r₀, r_z, and r_e structures for PF₃. The equilibrium structure is estimated to be P-F = 1.561 ± 0.001 Å and ∠FPF = 97.7 ± 0.2°.     

Intensities of rotational lines in first overtone bands for axially symmetric molecules of the group C3v

The interaction of vibration and rotation is considered in the computation of the intensities of rotational lines in the first overtone bands of axially symmetric molecules of the group C_3v. The calculation utilizes the contact transformation method through first order of approximation as outlines by Hanson and Nielsen. General formulas for the intensities of the lines in the first overtone bands 2ν_n and 2ν_m are obtained, where n and m denote normal modes of species A₁ and E, respectively. It is found that to this order of approximation the usual selection rules ΔJ = 0, ±1 and ΔK = 0 are observed for the parallel overtone band 2ν_n. For the overtone band 2ν_m, the selection rules are more complicated, being ΔJ = 0, ±1; Δl_m = 0 and ΔK = 0, Δl_m = ±2 and $\text{Δ}\text{K = ?1}$, or Δl_m = ±2 and ΔK = ±2.     

Infrared rotation-vibration spectra of ethane: The perpendicular band, ν7, of C2H6

The study of the gas-phase infrared spectrum of C₂H₆ in the region of the perpendicular CH-stretching band, ν₇, near 3000 cm^?1 is extended for the ΔK = + 1 subbands as far as K = 20. The spectral resolution of ～0.030 cm^?1 is increased to ～0.015 cm^?1 by deconvolution. The earlier investigation of this band for KΔK = +9 to ?5, is repeated with greater accuracy, providing more reliable ground-state constants (cm^?1): B₀ = 0.663089 ± 24, D₀^J = (0.108 ± 4) × 10^?5, D₀^JK = (0.50 ± 7) × 10^?5. The molecular constants (cm^?1) for the ν₇ fundamental are B₇ = 0.66310 ± 3, A₇ = 2.682, ν₀ = 2985.39, ζ₇ = 0.128. A discussion of resonance effects in this band, in particular x-y-Coriolis and Fermi resonance, is given.     

Inelastic collision cross section of excited molecules

The (v′=6,J′=43) level in theB ¹Π _u electronic state of Na₂ has been selectively populated by excitation with the 4 880 Å line of the argon laser. Through collisions with He atoms energy is transferred to neighbouring rotational states in Na₂ and the density of these states is determined by observing fluorescence to electronic ground state. From previous measurement of the lifetime of theB ¹Π _u state and new measurements of the intensities of collision induced spectral lines as a function of He pressure, absolute collision cross sections for all rotational transitions up to ΔJ=±5 have been obtained. The total cross section for all rotational transitions observed is σ _rot ^total =65±15 Ų. Preliminary results about collision induced vibrational transitions are also presented.     

Intensities of rotational lines in combination bands for axially symmetric molecules of the group C3v

The interaction of vibration and rotation is considered in the computation of the intensities of rotational lines in the combination bands of axially symmetric molecules of the group C_3v. The calculation utilizes the contact transformation method through first order of approximation as outlined by Hanson and Nielsen. General formulas for the intensities of the lines in the parallel combination band (ν_n + ν_n′) and perpendicular combination band (ν_m + ν_n) are obtained. It is found that to this order of approximation the usual selection rules ΔJ = 0, ±1 and ΔK = 0 are observed for the parallel combination band. For the perpendicular combination band the selection rules are more complicated, being ΔJ = 0, ±1, Δl_m = +1 and ΔK = +1 or ?2, Δl_m = ?1 and ΔK = ?1 or +2, Δl_m = ±3 and ΔK = 0. Specific intensity formulas are then given for the (ν₁ + ν₃) parallel and (ν₂ + ν₃) perpendicular combination bands of ammonia.     

Far infrared spectrum and spectroscopic constants of AsH3 in the ground state

The far ir spectrum of arsine, AsH₃, was recorded in the range 25–100 cm^?1 with a resolution of approximately 0.004 cm^?1. ΔJ = +1, ΔK = 0 rotational transitions were measured and assigned up to J″ = 12. These transitions, together with the presently available microwave and submillimeter-wave data and ground state combination differences, were analyzed on the basis of a rotational Hamiltonian which includes Δk = ±3 and Δk = ±6 interaction terms. The derived ground state molecular parameters reproduced the transition frequencies of both allowed and “perturbation allowed” transitions within the accuracy of the measurements. The equilibrium structure was determined for the AsH₃ molecule.     

Temperature dependence of foreign gas broadening of HCl fundamental lines

A long-pathlength variable temperature cell has been used to study three hydrogen chloride 0–1 vibration-rotational lines, P(7), P(8), and P(9) which were broadened by He, Ar, N₂, O₂, and CO at room temperature and by Ar at low temperatures down to 190 K. The method employed to extract the linewidths is the equivalent width method. The temperature dependence of the resulting cross sections for the HClAr broadened lines is similar to that recently found for other argon broadened HCl infrared and microwave lines. The results reported here (for high J lines) complement the other results (for low J lines) and together seem to constitute enough new data for further theoretical attempts at describing the process of collisional broadening in general, and the broadening of HCl by argon in particular.