Far infrared spectra of solid molecular nitrogen

This paper reports the observation of the far infrared absorption spectrum of a single crystal of N₂, measured over absorption paths of 4 cm (lengthwise) and 2 cm (across the crystal). The crystal chamber, with quartz windows, was immersed in a flow of cold helium gas. The spectrum from 20 to 120 cm^–1 was recorded in the liquid phase, the-phase, and over the full temperature range of the-phase (35.6–2.0 K) with a Fourier transform spectrometer. The spectral resolution, which was not instrument-limited, and the large path allowed the observation of more detailed multiphonon-transition structure in the spectrum of the-phase than has previously been observed.     

Perfluoroalkyl derivatives of nitrogen. Part LI [1]. Reaction of the N-halogenobistrifluoromethylamines (CF3)2NX (X=Cl,Br) with norbornadiene

Reaction of the amines (CF₃)₂NX (X=Cl,Br) with norbornadiene either in solvent (CH₂Cl₂) at ?78 °C in the dark or in the vapour phase at 20 °C in daylight gives a mixture of 3-halogeno-5-($\text{NN}$-bistrifluoromethylamino)nortricyclene ($\text{exo}$, $\text{endo}$-and $\text{exo}$, $\text{exo}$-isomers) and $\text{exo}$-5-($\text{NN}$-bistrifluoromethylamino)- $\text{anti}$-7-halogenonorbornene in quantitative yield formed $\text{via}$ halonium ion addition to the diene. The reaction of the amine (CF₃)₂NBr in solvent Me₂O or Et₂O at ?78 °C in the dark gives the same products in low yield, together with 3-bromo-5-alkoxynortricyclene ($\text{exo}$, $\text{endo}$- and $\text{exo}$, $\text{exo}$-isomers) and the amine (CF₃)₂NR (R=Me, Et) in high yield.     

Theoretical Study of the Collision-Induced Double Transition CO(2) (nu(3) = 1) + N(2) (nu(1) = 1) <-- CO(2) (nu(3) = 0) + N(2) (nu(1) = 0) at 296 K

A procedure is presented for the calculation of the double vibrational collision-induced absorption CO(2) (nu(3) = 1) + N(2) (nu(1) = 1) <-- CO(2) (nu(3) = 0) + N(2) (nu(1) = 0) on the basis of quantum lineshapes computed using an isotropic potential and dipole-induced dipole functions. The linestrengths and energies of the vibration-rotation transitions are treated explicitly for N(2), utilizing the HITRAN database for CO(2). The theoretical absorption profile is compared to recent experimental results. By narrowing the width of the individual lines contributing to the overall absorption profile relative to their values determined for N(2)-N(2) collision-induced absorption, excellent agreement between theory and experiment is obtained. Copyright 2000 Academic Press.     

Theoretical Herman-Wallis coefficients for C70 and D70 and the dipole-moment function of HCl

Theoretical expressions for the Herman-Wallis coefficients C⁷₀ and D⁷₀ and a correction term of order 2B_e/ω_e times the leading term for C⁶₀ have been derived in terms of the Dunham potential-energy parameters and series dipole-moment expansion coefficients by the method of computer algebra. After reviewing previous work on the extraction of the dipole-moment function for HCl from experimental data, the present results are applied to a determination of the series representation up to seventh order in the reduced displacement from the equilibrium internuclear separation. Coefficients for an alternate representation in terms of a Padé approximant are also obtained; this model dipole-moment function should enable one to estimate more accurately the higher overtone and highly excited hot-band intensities since it circumvents the divergence difficulties of the series expansion and has the correct asymptotic behavior at both small and large internuclear separations.     

CO 1-0 band isotopic lines as intensity standards

Fundamental band vibration-rotational line intensities are reported for the¹²C¹⁶O, ¹³C¹⁶O, and ¹²C¹⁸O molecules. The intensities were computed using numerically obtained matrix elements of a recently determined electric dipole moment function. We also report new intensity measurements for some of these lines obtained via high-resolution Fourier spectra. The overall consistency (≈2.2%) between our calculations, which are based on recent experimental determinations of CO 1-0 band intensities, not including our own, and our independent experimental results suggests that the lines of the fundamental band of CO can be used as absolute intensity standards.     

Classical treatment of vibration-rotation intensities for the Morse oscillator

The effect of vibration-rotation interaction on spectral line intensities is treated classically for the Morse oscillator. To describe the distribution of intensity in the R and P branches, one must take into account both the vibrational (radial) and the rotational (perpendicular) dipole moment functions. When this is done, the leading terms for the Fourier coefficients of these functions, as well as the Herman-Wallis factors, agree exactly with the corresponding quantum mechanical matrix elements in the Dunham limit.