Revised IR spectrum, radiative efficiency and global warming potential of nitrogen trifluoride

Nitrogen trifluoride (NF3) is an industrial gas used in the semiconductor industry as a plasma etchant and chamber cleaning gas. NF3 is an alternative to other potent greenhouse gases and its usage has increased markedly over the last decade. In recognition of its increased relevance and to aid planning of future usage we report an updated radiative efficiency and global warming potentials for NF3. Laboratory measurements give an integrated absorption cross section of 7.04 x 10(-17) cm(2) molecule(-1) cm(-1) over the spectral region 200 2000 cm(-1). The radiative efficiency is calculated to be 0.21 Wm(-2) ppbv(-1) and the 100 year GWP, relative to carbon dioxide, is 17200. These values are approximately 60% higher than previously published estimates, primarily reflecting the higher infrared absorption cross-sections reported here.

Coriolis interactions about x-y axes in symmetric tops

Selection rules and matrix elements are derived for Coriolis interactions between vibrational levels due to rotation about (x, y) axes in symmetric top molecules. The theory is developed in detail for the case of interaction between an A1 and an E species vibrational level in a C3v molecule; perturbations to both the positions and the intensities of the rovibration transitions in the spectrum are considered. A computer program has been written which calculates exactly the perturbed spectrum of two interacting rovibration bands according to this model, the results being presented directly by a graph plotter connected to the computer. This has been used to interpret perturbations observed in two pairs of interacting fundamentals in the spectrum of CH3F (ν2 - ν5 and ν3 - ν6) and one pair in CD3Cl (ν2 - ν5). The resulting analysis of the observed spectrum leads to new values for some vibration-rotation interaction constants and also leads to a unique determination of the sign relationship between the dipole moment derivatives in each pair of interacting normal vibrations. These sign relations are summarized in Figs. 8, 12, and 15.

Coriolis perturbations in the infrared spectrum of ethylene

Rotational structure has been resolved and analyzed in two of the infrared‐active perpendicular bands of C2H4 vapor: the Type b fundamental band, ν10, at 826 cm—1, and the Type c fundamental band, ν7, at 949 cm—1. Many of the individual PP and RR branch lines have been observed. The analysis has been confined to values of the quantum number K≥3, for which energy levels ethylene shows no detectable deviations from a symmetric‐top rotational structure. The analysis reveals a Coriolis interaction between ν7 and ν10, and between ν4 and ν10, and values of the Coriolis constants ζ7,10z and ζ4,10y are obtained; these are related to normal coordinate calculations for the appropriate symmetry species, and force constants are derived to fit the observed zeta constants. The band center of ν10 has been revised from the original figure of 810 cm—1 to the new value, 826 cm—1, and the inactive frequency ν4 is estimated to lie at 1023±3 cm—1, in good agreement with the previous estimate of 1027 cm—1. The change in the value of ν10 leads to a suggested change in the value of the Raman‐active fundamental ν6 from 1236 to 1222 cm—1. New combination bands have been observed at 2174 cm—1, assigned as ν3+ν10; and at 2252 cm—1, assigned as ν4+ν6; also rotational structure has been resolved and analyzed in the ν6+ν10 band at 2048 cm—1. The new data obtained for the C2H4 molecule are summarized in Table XII, with all of the other data presently available on the vibrational and rotational constants.

A refined quartic forcefield for acetylene: accurate calculation of the vibrational spectrum

It is now possible to calculate the nine-dimensional rovibrational wavefunctions of sequentially bonded four-atom molecules variationally without dynamical approximation. In the case of HCCH, the simplest such molecule, many hundreds of rovibrational (J = 0, 1, 2) levels can be converged to better than 1.5 cm −1. Variational calculations of this kind are used here systematically to refine the well-known quartic valence-coordinate forcefleld of Strey and Mills [J.Mol. Spectrosc.59, 103-115 (1976)] against experimental term values up to three C-H stretch quanta for the principal and two deuterated isotopomers, yielding a new surface that reproduces the energies of all the known Σ, Π, and Δ states of these species up to the energy of two C-H stretch quanta with an rms error of 3 cm−1 . The refined forcefield is used to study the resonances associated with the accidental degeneracies (ν2 + ν4 + ν5, ν3) and (ν2 + 2ν5, ν1) in the principal isotopomer, leading to a clarification of the assignment of she experimentally detected states in the 2ν3 and 3ν3, polyads, and to the finding that vibrational Coriolis (kinetic energy) terms, rather than quartic anharmonicities in the potential, are the primary cause of the resonant interactions. Using a new cubic ab initio electric dipole field to calculate IR absorption coefficients, 24 undetected Σ and Π states of 1H12C12C1H and 5 undetected Σ states of D12C12CD are identified as candidates for experimental study, and their calculated energies and assignments are given.

Microwave spectrum of CHD2CN and CHD2NC, and the harmonic force field and rz structure of methyl cyanide and isocyanide

The microwave spectra of CHD2CN and CHD2NC have been measured from 18 to 40 GHz; about 20 type A and 30 type C transitions have been observed for each molecule. These have been fitted to a Hamiltonian using 3 rotational constants, and 5 quartic and 4 sextic distortion constants, in the IrS reduction of Watson [in “Vibrational spectra and structure” Vol. 6 (1977)]; the standard error of the fit is 26 kHz. For methyl cyanide the 5 quartic distortion constants have been used to further refine the recent harmonic force field of Duncan et al. [J. Mol. Spectrosc. 69, 123 (1978)], but the changes are small. Finally, for both molecules, the harmonic force field has been used to determine zero point average moments of inertia Iz from the ground state rotational constants for many isotopic species, and these have been used to determine an rz structure. The results are compared with rs structure calculations.

The two-dimensional anharmonic oscillator II: the microwave spectrum of silyl isocyanate, SiH3NCO

The J + 1 ← J transitions (J = 2, 3, 4, 5, and 6) in the microwave spectrum of SiH3NCO have been assigned for the vibrational ground state and for the vibrational states v10 = 1, 2, and 3. The results for v10 = 0 confirm earlier work. The vibration-rotation constants show a remarkable variation with v10 and l10. To a large extent the anomalous behavior of these constants has been explained in terms of a strongly anharmonic potential function for the ν10 vibrational mode.