Absolute wavenumber measurements of 1-0, 2-0, HF and 2-0, H35Cl,H37Cl absorption bands

Fourier absorption spectra of HCl and HF at room temperature permitted to measure 87 absolute wavenumbers. The absolute observed position of the P(6) line of the 1-0 band of HF is not in agreement with a recent heterodyne determination [3]. It is found equal to 110 725 739 ± 7.5 MHz.     

Pressure broadening in the 0–4 through 0–7 overtone bands of H35Cl and H37Cl

We have measured the pressure broadening coefficients of a number of rotation-vibration lines in the 0–4 through 0–7 overtone bands of HCl utilizing a Fourier transform spectrometer and a 409 m path length White cell. These data, when included with previous measurements on the fundamental and lower overtone bands, show a systematic variation of pressure broadening with increasing overtone band. This result reflects a change in the collision dynamics between molecules in the upper state of the transition with ground state molecules.     

Widths and shifts of H35Cl lines in the fundamental band induced by argon and xenon at low temperatures

We have measured, at high resolution (0.024cm^-1), the linewidths and shifts in the fundamental band of H³⁵Cl broadened by argon (up to 5 bars) and xenon (up to 4 bars) at low temperatures (between 298 and 163 K). The experimental results have been compared with calculated data derived from the Anderson-Tsao-Curnutte theory using the Tipping-Herman potential.     

Determination of A0 for CH335Cl and CH337Cl from the ν4 infrared and Raman bands

The ν₄ infrared and Raman bands of CH₃Cl were analyzed simultaneously. A direct fit yielded a complete set of constants for CH₃³⁵Cl, including A₀ = 5.20530 ± 0.00010 cm^?1 and D_K = (8.85 ± 0.13) × 10^?5cm^?1. For CH₃³⁷Cl an incomplete set of constants was obtained from the infrared band, and A₀ = 5.2182 ± 0.0010 cm^?1 was estimated by curve fitting of the Raman spectrum. The resulting equilibrium structure is $\text{r(}\text{CH) = 1.0854 ± 0.0005}\text{A}\text{?}$, $\text{r(}\text{CCl) = 1.7760 ± 0.0003}\text{A}\text{?}$, and <(HCH) = 110°.35 ± 0°.05.     

10-μm sub-doppler laser-Stark spectroscopy of methyl chloride: Analysis of the ν6 bands of the CH335Cl and CH337Cl

About 900 Stark transitions from 70 vibration-rotation transitions in CH₃³⁵Cl and about 400 transitions from 38 transitions in CH₃³⁵Cl in the ν₆ band have been assigned. These data were analyzed simultaneously with previously published microwave data on the ν₆ = 1 state. The fit has a standard deviation of about 2 MHz for the data for both isotopes. The isoptopic shift ν₆35 ? ν₆37 = 0.3766(6) cm^?1. Rotational dependence of the dipole moment was also just apparent at about μ_J = μ_K = 1 × 10^?5 D, and a complete set of molecular constants is given.     

Temperature dependence of rare gas broadening and shifting of first harmonic lines of H35Cl

Widths and shifts of HCl vibration-rotation lines, pressurized by rare gases, have been measured for the 0–2 band as functions of temperature. The results reported here complement previously published results on the fundamental band. The model of Smith, Giraud and Cooper is used to calculate widths and shifts; good agreement is obtained between experiment and theory. Problems concerning the accuracy of available potential energy surfaces and the calculation of differential cross sections are discussed briefly.     

Rotational analysis of the B3Π(0+) → X1Σ+ band systems of 35Cl35Cl and 35Cl37Cl in the chlorine afterglow emission spectrum

The B³Π(0⁺) → X¹Σ⁺ band system of Cl₂, excited by the recombination of ground state $\text{Cl}{}^2\text{P}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ atoms at total pressures near 2 Torr, has been rotationally analyzed in the range 6300–9900 Å. About 30 bands, with 0 ≤ v′ ≤ 6 and 5 ≤ v″ ≤ 14, were investigated, mostly for both ³⁵Cl³⁵Cl and ³⁵Cl³⁷Cl. The band origins and rotational constants for the B state were obtained with the help of the known constants for the ground state. The principal molecular constants (cm^?1) for the B³Π(0⁺) state of ³⁵Cl³⁵Cl are as follows: T_e′ = 17 817.67(3); ω_e′ = 255.38(3); ω_e′x_e′ = 4.59(1); ω_e′y_e′ = ?0.038(8); D_e′ = 3341.17(14); B_e′ = 0.16313(3); α_e′ = 2.42(3) × 10^?3; γ_e′ = ?5.7(7) × 10^?5. The equilibrium internuclear separation is 2.4311(2) Å. The results of Briggs and Norrish on a transient absorption spectrum of Cl₂ assigned as $\text{0}{}_{\mathrm{g}}{}^{\mathrm{+}}\text{← B}{}^3\text{Π}\text{(0}{}^{\mathrm{+}}\text{)}$ are reinterpreted with the present constants.     

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.     

Pure rotational spectra of 32SF535Cl, 32SF537Cl,and 34SF535Cl up to 300 GHz

Pure rotational spectra of the three molecules ³²SF₅³⁵Cl, ³²SF₅³⁷Cl, and ³⁴SF₅³⁵Cl in their ground vibrational states have been observed up to 300 GHz (8 < J < 80). Molecular parameters have been computed with good accuracy for the three isotopic species. The “K-type” splitting characteristic of molecules belonging to the C_4v symmetry group has been clearly seen and measured.     

The measurement of pressure-induced shifts of the J = 0 → 1 transition of CH3Cl35 at various temperatures

Temperature behavior of the rotational resonance (J = 0 → 1, F = 3/2→5/2) transition of CH₃Cl³⁵ under various pressures was investigated over a range of 193 ≤ T ≤ 366K using a source-modulated spectrometer to ascertain how the central resonance shifted as the perturbing gas pressure within the absorption cell was varied. Frequency shifts were determined for measured pressures of 1 ≤ P ≤ 30mTorr for the temperature range specified. Experimental results are compared with recent theoretical calculations.     

The emission spectra of H35Cl+, H37Cl+, D35Cl+, and D37Cl+ in the region 2700–4100 Å

The $\text{A}{}^2\text{Σ}{}^{\mathrm{+}}\text{-X}{}^2\text{Π}$ emission spectrum of HCl⁺ has been measured and analyzed for four isotopic combinations. These analyses extend previous work and provide rotational constants for the v = 0–2 levels of the ground state and for the v = 0–9 levels of the excited state. RKR potentials have been determined for both states, although the upper state could not be fitted precisely to such a model. Calculated relative intensities based on these potentials demonstrated that the electronic transition moment must change rapidly with lower state vibrational quantum number. Although considerable caution should be exercised in applying the concept of equilibrium constants to the $\text{A}{}^2\text{Σ}{}^{\mathrm{+}}$ state, the following are the best estimates of these constants (in cm^?1) for the $\text{X}{}^2\text{Π}$ state of H³⁵Cl⁺: B_e = 9.9406, ω_e = 2673.7, A_e = ? 643.7, and $\text{r}{}_{\mathrm{e}}\text{= 1.315}\text{A}\text{?}$. For the $\text{A}{}^2\text{Σ}{}^{\mathrm{+}}$ state of H³⁵Cl: T_e = 28 628.08, B_e ～ 7.505, ω_e ～ 1606.5, and $\text{r}{}_{\mathrm{e}}\text{= 1.514}\text{A}\text{?}$.     

Investigation of the reaction 37Cl(n, γ)38Cl

With Ge(Li) detectors the γ-radiation following thermal-neutron capture in natural and in ³⁷Cl enriched targets was studied. A total of 79 γ-lines has been assigned to the ³⁷Cl(n, γ) reaction and 64 of these lines have been placed in a decay scheme of ³⁸Cl. The excitation energies of 24 bound states of ³⁸Cl have been determined with 0.09–1.2 keV errors. The neutron separation energy of ³⁸Cl is 6107.7 ± 0.4 keV. A strong correlation between reduced stripping widths and (n, γ) primary reduced widths was found for the l_n(d, p) = 1 states if, instead of the Weisskopf reduction factor E_γ^?3, a factor E_γ^?1.2 was used.     

The ν6 band of CF235Cl37Cl from IR-MW double resonance

Effective constants for the ν₆ band of CF₂³⁵Cl³⁷Cl have been determined from the analysis of infrared-microwave double-resonance data.     

Absolute frequency measurements of the 0002-0000, 2001-0000, and 1201-0000 bands of N2O by heterodyne spectroscopy

The absolute frequencies of 39 lines in the 00⁰2-00⁰0, 20⁰1-00⁰0, and 12⁰1-00⁰0 bands of N₂O in the range 4300–4800 cm^?1 have been measured by heterodyne frequency techniques. The lines were each measured in Doppler-limited absorption, with a color-center laser as a tunable probe of the N₂O and two stabilized CO₂ lasers as reference frequencies. New rovibrational constants have been fitted to these measurements. Tables of calculated transition frequencies are given, with estimated absolute uncertainties as small as 10^?4 cm^?1. The pressure shifts of four lines have been measured, and the values fall within the range of 0 to ?2 MHz/kPa (0 to ?0.2 MHz/Torr).     

Vibrational spectra and force constants of symmetric tops: ν1, ν5, and 2ν5 of CF335Cl and CF337Cl

The gas phase infrared spectra of CF₃³⁵Cl and CF₃³⁷Cl have been recorded in the ν₁ region and 2ν₅ regions with a resolution of 0.09 cm^?1. Additionally the ν₅ fundamental of CF₃Cl, with natural isotopic abundance, has been reinvestigated with a resolution of approximately 0.36 cm^?1. Molecular constants have been evaluated from the observed spectra by means of polynomials and band contour simulation. The possibility of a Fermi resonance between ν₁ and 2ν₅ is discussed.     

Vibrational spectra and force constants of symmetric tops: Rotational analysis of ν3 and 2ν3 of H3Si35Cl and H3Si37Cl

The gas-phase infrared spectra of natural and ³⁵Cl isotopically enriched H₃SiCl have been recorded with a resolution of 0.04 cm^?1 in the regions of ν₃ (～550 cm^?1) and 2ν₃ (～1100 cm^?1). The fundamentals of species with ²⁸Si, ²⁹Si, ³⁰Si, ³⁵Cl, and ³⁷Cl and several hot bands of the series nν₃ + mν_i ? mν_i (n, m = 1, 2; i = 3 and 6) have been detected. The parameters ν₀, x₃₃, x₃₆, B₀, α₃^A, D_J⁰ and D_J³ were determined by a combination of least-squares analysis of P and R branches resolved into J peaks (J ≤ 90) and a band contour simulation. Possible resonances of nν₃ and (n ? 1)ν₃ + ν₆ are discussed.     

Investigations in (0-0) isotopic bands of the C2 Swann system

Employing the various isotopes of carbon, (0-0) bands of the C₂ Swann system have been investigated. Comparisons have been made between the observed rotational line positions and those obtained by computer calculations with the respective constants evaluated from ¹²C₂. There is a good agreement (within ± 0.5 cm^?1 in most of the cases) between the two sets of values. The studies include the effect of change of nuclear mass and spin on different aspects of rotational structure and intensity pattern.     

High-resolution infrared spectrum and analysis of the ν1 band of CF337Cl

The rotational structure of CF₃³⁷Cl ν₁ band has been investigated using spectra of trifluorochloromethane in natural isotopic abundance, recorded with a tunable diode laser spectrometer. The spectra analyzed have been obtained by keeping the sample at low temperature (～200 K) to minimize the strong interference arising from “hot” band transitions. The K structure of many P(J) and R(J) multiplets has been resolved and positively identified: the maximum J value reached in the P and R branches was 38 and 40, respectively. About 650 unblended lines have been used for the least-squares fit to the energy expression including the quartic centrifugal distortion coefficients. Molecular constants for the ν₁ band of CF₃³⁷Cl have been derived. A weak perturbation affecting the rotational levels with K = 18 and J′ ≥ 36 has also been observed.     

Strengths of (p, γ) resonances in 33Cl, 35Cl and 28Si

Absolute strength measurements have been performed for the E_p = 580 and 588 keV ³²S(p,γ)³³Cl, E_p = 1214keV³⁴S(p,γ)³⁵Cl and E_p = 633 and 744 keV²⁷Al(p,γ)²⁸Si resonances with a Ge(Li) detector. Results are discussed with regard to the decay of isobaric analog resonances in ³⁵Cl and ³⁷Cl.     

Self-broadening and shifting of HI lines in the 1-0 and 2-0 infrared bands

Pressure-broadening and -shifting coefficients of pure HI at room temperature have been determined from fits of high-resolution Fourier transform spectra in the fundamental and first overtone infrared bands. The results indicate that the measured widths are almost identical in both bands and decrease significantly with the rotational quantum number. On the contrary, the pressure-induced shifts show a strong dependence on both the rotational and vibrational states. These results are compared with predictions of a semi-classical model. The latter leads to calculated values in good agreement with measurements and shows that the broadening is dominated by electrostatic interactions due to the (permanent) electric dipole and quadrupole moments. On the contrary, the observed shifts cannot be explained without the introduction of a significant vibrationally dependent isotropic potential. The effects of line coupling between hyperfine components are also discussed although they are expected to be small and cannot be observed from the measured spectra. Finally, some tabulated values of calculated widths and shifts vs. quantum numbers and temperature are proposed. They should be useful for infrared sounding of HI amounts, particularly in the monitoring of the hydrogen production through the sulfur-iodine thermochemical cycle.