Retrieval of effective ice crystal size in the infrared: sensitivity study and global measurements from TIROS-N Operational Vertical Sounder

The difference between cirrus emissivities at 8 and 11 μm is sensitive to the mean effective ice crystal size of the cirrus cloud, De. By using single scattering properties of ice crystals shaped as planar polycrystals, diameters of up to about 70 μm can be retrieved, instead of up to 45 μm assuming spheres or hexagonal columns. The method described in this article is used for a global determination of mean effective ice crystal sizes of cirrus clouds from TOVS satellite observations. A sensitivity study of the De retrieval to uncertainties in hypotheses on ice crystal shape, size distributions, and temperature profiles, as well as in vertical and horizontal cloud heterogeneities shows that uncertainties can be as large as 30%. However, the TOVS data set is one of few data sets which provides global and long-term coverage. Having analyzed the years 1987–1991, it was found that measured effective ice crystal diameters De are stable from year to year. For 1990 a global median De of 53.5 μm was determined. Averages distinguishing ocean/land, season, and latitude lie between 23 μm in winter over Northern Hemisphere midlatitude land and 64 μm in the tropics. In general, larger Des are found in regions with higher atmospheric water vapor and for cirrus with a smaller effective emissivity.

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.

Rotational spectra induced by vibrations

Mizushima and Venkateswarlu showed in 1953 that certain molecules have the property that excited vibrational states may possess rotational spectra even when the rotational spectrum of the ground vibrational state is forbidden by symmetry. We call such a spectrum a vibrationally induced rotational spectrum, and have made a systematic examination of the point groups which permit such behaviour. We also give formulae for the approximate line frequencies and intensities in these spectra, and discuss some of the problems involved in observing them. The spectra can only arise from degenerate vibrational states, and are of three possible types: i) symmetric top perpendicular spectra, shown by molecules belonging to the point groups Dnh, Dn and Cnh, where n is odd; (ii) symmetric top parallel spectra, shown by molecules belonging to Dnd and S2n, where n is even; and (iii) spherical top spectra, shown by molecules belonging to T or Td. Excited vibrational states of polar molecules of point groups Cnv or Cn, where n is odd, may also possess vibrationally induced perpendicular components of type (i), in addition to their ordinary parallel spectra. In addition to the above limitations on the point groups there are, in general, limitations on the symmetry species of the degenerate vibrational states.

Microwave spectra and centrifugal distortion constants of oxetane

The microwave spectra of oxetane (trimethylene oxide) and its three symmetrically deuterated isotopic species have been observed on a Hewlett-Packard microwave spectrometer from 26.5 to 40 GHz. For the parent species, the β-d2 and the αα′-d4 species, about 300 lines have been assigned for each molecule, and for the d6 species more than 600 lines have been assigned. The assignments range from v = 0 to v = 5 in the puckering vibration; although they are mostly Q transitions, either 3 or 4 R transitions have been observed for each vibrational state. The spectra have been interpreted using an effective rotational hamiltonian for each vibrational state, including five quartic distortion constants according to Watson's formulation, and a variable number of sextic distortion constants; in general, the lines are fitted to about ± 10 kHz. The distortion constants show an anomalous zig-zag dependence on the puckering vibrational quantum number, similar to that first observed for the rotational constants by Gwinn and coworkers. This is interpreted according to a simple modification of the standard theory of centrifugal distortion, involving the double minimum potential function in the puckering coordinate.

The two-dimensional anharmonic oscillator III: the CCC bending mode of C3O2

Newly observed data on the rotational constants of carbon suboxide in excited vibrational states of the low-wavenumber bending vibration ν7 have been successfully interpreted in terms of the two-dimensional anharmonic oscillator wavefunctions associated with this vibration. By combining these results with published infrared and Raman spectra the vibrational assignment has been extended and a refined bending potential for ν7 has been derived: this has a minimum at a bending angle of about 24° at the central C atom, with an energy maximum at the linear configuration some 23 cm−1 above the minimum. From similar data on the combination and hot bands of ν7 with ν4 (1587 cm−1) and ν2 (786 cm−1) the effective ν7 bending potential has also been determined in the one-quantum excited states of ν4 and ν2. The effective ν7 potential shows significant changes from the ground vibrational state; the central hump in the ν7 potential surface is increased to about 50 cm−1 in the v4 = 1 state, and decreased to about 1 cm−1 in the v2 = 1 state. In the light of these results vibrational assignments are suggested for most of the observed bands in the infrared and Raman spectra of C3O2.

Excited vibrational state microwave spectra, structure, and force-field of trifluorosilane

The J = 2−1 microwave spectrum of six isotopic species of HSiF3 has been observed and assigned in excited states of five of the six fundamental vibrations. The assignment is based on relative intensities, double resonance experiments, and trial anharmonic force constant calculations. Analysis of the spectra leads to experimental values for five of the constants, all three l-doubling constants qt, one Fermi resonance constant φ233, and one zeta constant. The harmonic force field has been refined to all the available data on vibration wavenumbers, centrifugal distortion constants, and zeta constants. The cubic anharmonic force field has been refined to the data on and qt constants, using two models: a valence force model with two cubic force constants for SiH and SiF stretching, and a more sophisticated model. With the help of these calculations, the following equilibrium structure has been determined: re(SiH) = 1.4468(±5) Å, re(SiF) = 1.5624(±1) Å, HSiF = 110.64(±3)°,

Vibration-rotation spectra of monofluoroacetylene: 1700 to 7500 cm−1

High-resolution vibration-rotation spectra of monofluoroacetylene are reported for many bands in the region 1700 to 7500 cm−1. The spectra were observed on Nicolet 7199 and Bruker IFS 120 Fourier spectrometers, with resolutions of about 0.06 and 0.003 cm−1, respectively. About 130 bands have been observed in this region, of which about 80 have been rotationally analyzed. The assignment of vibrational labels to the higher energy levels is complicated by the effects of strong Fermi resonances, and many weak localized rotational resonances are observed.

Overtone spectra and anharmonic resonances in the haloacetylenes

In this work preliminary results are reported on an extensive vibrational analysis of the molecules HCCX and DCCX with X = F and Cl, in which a number of anharmonic resonances are analysed. The importance of quartic anharmonic resonances in these molecular types is reported involving the effective constants K1244 and K1255, and these are related to the corresponding resonances in acetylene and its isotopomers. The correct analysis of Fermi resonances and quartic anharmonic resonances is important not only in reproducing the high overtone energy levels, but also in fitting the observed rotational constants, and in determining the αr constants and hence the equilibrium rotational constants. In this paper we revise our recent analysis of the equilibrium structure of HCCF in the light of these effects.

Vibration-rotation spectra and the harmonic force field of HOCl

Vibration-rotation spectra of HOCl have been measured at a resolution of 0.05 cm−1 to determine vibration rotation constants, and 35–37 Cl isotope shifts in the vibration frequencies. The spectrum of DOCl has also been recorded, and a preliminary analysis for the band origins has been made. The vibrational frequency data and centrifugal distortion constants have been used to determine the harmonic force field in a least-squares refinement; the force field obtained also gives a good fit to data on the vibrational contributions to the inertial defect. The equilibrium rotational constants of HOCl have been obtained, and an equilibrium structure has been estimated.

Carbon suboxide: the infrared spectrum from 1800 to 2600 cm-1

The infrared spectrum of carbon suboxide has been recorded from 1800 to 2600 cm−1 at a resolution of 0.003 cm−1. About 7% of the ca. 40 000 lines observed have been assigned and analyzed, belonging to 36 different bands. Most of these are associated with the fundamental ν3, at 2289.80 cm−1, and the combination band ν2 + ν4, at 2386.61 cm−1, each of which give rise to a system of sum bands, difference bands, and hot bands involving the low-wave-number fundamental ν7 at 18 cm−1. A few other tentative assignments are made. The bands have been analyzed for vibrational and rotational constants.

The infra-red spectra of silyl fluoride and silyl fluoride-d3

Infra-red spectra have been recorded for silyl fluoride and silyl fluoride-d3 at a resolution of circa 0·3 cm-1. Rotational structure has been observed for parallel fundamentals in both molecules, and for all perpendicular fundamentals. In both SiH3F and SiD3F the A1 and E species deformation modes interact strongly via a Coriolis perturbation; this has been analysed, and the band origin of v5 for SiH3F is reassigned. A hybrid-orbital force field based on the experimental data is also reported.

The infrared spectrum of silicon difluoride

The infrared spectrum of the stretching fundamentals of SiF2 has been obtained at a resolution of ≈ 0.1 cm−1 using a FTIR spectrometer. The spectrum has been analysed using computer simulation based on a coupled hamiltonian for v1 and v3, giving v1 = 855.01 cm−1 and v3 = 870.40 cm−1. The relative magnitude and sign of the vibrational transition moments has been determined from the ξC13 Coriolis coupling.