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Giver, L. P.

Publications and source records attributed to Giver, L. P..

At least 19 records

Uncertainties of the Intensity of the 1130 nm Band of Water Vapor

Belmiloud, et al have recently suggested that the HITRAN line intensities in the 1130 nm water vapor band are much too weak. Giver, et at corrected unit conversion errors to make the HITRAN intensities compatible with the original measurements of Mandin, et al, but Belmiloud, et al believe that many of those line intensity measurements were too weak, and they propose the total intensity of the 1130 nm water vapor band is 38% stronger than the sum of the HITRAN line intensities in this region. We have made independent assessments of this proposal using 2 spectra obtained with the Ames 25 meter base path White cell. The first was made using the moderate resolution (8 nm) solar spectral flux radiometer (SSFR) flight instrument with a White cell absorbing path of 506 meters and 10 torr water vapor pressure. Modeling this spectrum using the HITRAN linelist gives a reasonable match, and the model is not compatible when the HITRAN line intensities are increased by 38%. The second spectrum was obtained with a White cell path of 1106 meters and 12 torr water vapor pressure, using a Bomem FTIR with near Doppler width resolution. This spectrum is useful for measuring intensities of isolated weak lines to compare with the measurements of Mandin, et al. Unfortunately, as Belmiloud et al point out, at these conditions the strong lines are much too saturated for good intensity measurements. Our measurements of the weak lines are in reasonable agreement with those of Mandin, et al. Neither of our spectra supports the proposal of Belmiloud et al for a general 38% increase of the absorption intensity in the 1130 nm water vapor band.

Giver, L. P.↗

Absolute Rovibrational Intensities, Self-Broadening and Self-Shift Coefficients for the X(sup 1) Sigma(+) V=3 (left arrow) V=0 Band (C-12)(O-16)

The rotationless transition moment squared for the x(sup 1) sigma (sup +) v=3 (left arrow) v=0 band of CO is measured to be the absolute value of R (sub 3-0) squared = 1.7127(25)x 10(exp -7) Debye squared. This value is about 8.6 percent smaller than the value assumed for HITRAN 2000. The Herman-Wallis intensity factor of this band is F=1+0.01168(11)m+0.0001065(79)m squared. The determination of self-broadening coefficients is improved with the inclusion of line narrowing; self-shifts are also reported.

Chackerian, Charles, Jr.↗

Absolute Rovibrational Intensities for the Chi(sup 1)Sigma(sup +) v=3 <-- 0 Band of (12)C(16)O Obtained with Kitt Peak and BOMEM FTS Instruments

This work was initiated to compare absolute line intensities retrieved with the Kitt Peak FTS (Fourier Transform Spectrometer) and Ames BOMEM FTS. Since thermal contaminations can be a problem using the BOMEM instrument if proper precautions are not taken it was thought that measurements done at 6300 per cm would more easily result in satisfactory intercomparisons. Very recent measurements of the CO 3 <-- 0 band fine intensities confirms results reported here that the intensities listed in HITRAN (High Resolution Molecular Absorption Database) for this band are on the order of six to seven percent too low. All of the infrared intensities in the current HITRAN tabulation are based on the electric dipole moment function reported fifteen years ago. The latter in turn was partly based on intensities for the 3 <-- 0 band reported thirty years ago. We have, therefore, redetermined the electric dipole moment function of ground electronic state CO.

Chackerian, Charles, Jr.↗

Line Assignments and Position Measurements in Several Weak CO2 Bands Between 4590/cm and 7930/cm

A substantial set of CO2 spectra from 4500 to 12000/cm has been obtained at Ames with 1500 m path length using a Bomem DA8 FTS. The signal/noise was improved compared to prior spectra obtained in this laboratory by including a filter wheel limiting the band-pass of each spectrum to several hundred per cm. We have measured positions of lines in several weak bands not previously resolved in laboratory spectra. Using our positions and assignments of lines of the Qbranch of the 31103-00001 vibrational band at 4591/cm, we have redetermined the rotational constants for the 31103f levels. Q-branch lines of this band were previously observed, but misassigned, in Venus spectra by Mandin. The current HITRAN values of the rotational constants for this level are incorrect due to the Q-branch misassignments. Our prior measurements of the 21122-00001 vibrational band at 7901/cm were limited to Q-and R-branch lines; with the improved signal/noise of these new spectra we have now measured lines in the weaker P branch. The 21122 (Gv = 790148/cm) levels are known to be perturbed by the 32211 (G(sub v) = 789757/cm) levels; new DND calculations predict that high-J lines of the forbidden 32211-00001 vibrational band 'borrow' intensity from the corresponding transitions of the 21122-00001 band. We have identified such Q- and R-branch transitions of the 32211-00001 band from 26 < J" < 44, based on our position measurements of lines in the 32211-02201 band at 6562/cm.

Giver, L. P.↗

Line Assignments and Position Measurements in Several Weak CO2 Bands between 4590 /cm and 7930/ cm

A substantial set of CO2 spectra from 4500 to 12000 /cm has been obtained at Ames with 1500 m path length using a Bomem DA8 FTS. The signal/noise was improved compared to prior spectra obtained in this laboratory by including a filter wheel limiting the band-pass of each spectrum to several hundred/cm. We have measured positions of lines in several weak bands not previously resolved in laboratory spectra. Using our positions and assignments of lines of the Q branch of the 31103-00001 vibrational band at 4591/cm, we have re-determined the rotational constants for the 31103f levels. Q-branch lines of this band were previously observed, but misassigned, in Venus spectra by Mandin. The current HITRAN values of the rotational constants for this level are incorrect due to the Q-branch misassignments. Our prior measurements of the 21122-00001 vibrational band at 7901/cm were limited to Q- and R-branch lines; with the improved signal/noise of these new spectra we have now measured lines in the weaker P branch.

Giver, L. P.↗

The NO Vibrational Fundamental Band: O2-Broadening Coefficients

Rovibrational spectra of the vibrational fundamental of nitric oxide at 1875 cm-1 have been recorded under O2-broadening conditions at 296 K and 0.0056 cm-1 resolution using the Solar Nemeth FTS at the Kitt Peak National Observatory. The use of a flow system, which maintains the NO2 at trace levels, has enabled the first measurement of these broadening coefficients. The broadening of the trace contaminant, N2O, allowed checks of the measured pressures. The least-squares analysis of the spectra includes the nuclear hyperfine structure in addition to (lambda) doubling. We observed differential broadening between the e and f (lambda) components of 2II 1/2 transitions as well as larger differences in broadening observed between 2II3/2 transitions.

Freedman, R. S.↗

Zeeman Tuning Rates in the v3 Band of NO2

Zeeman spectra of the v3 fundamental (at approximately 1620 c/m) of nitrogen dioxide (14N02) have been recorded with magnetic fields of approximately 500 Gauss using a FTS (at the Kitt Peak National Observatory), as well as a tunable diode laser. At low magnetic fields the Zeeman effect is small compared to the spin-rotation interaction, and the Zeeman tuning rates are expected to be linear with magnetic field. Measured tuning rates of the Q-branch (KA = 2 - 9, N = 2 - 6) sigma transitions are compared to those expected for 2Sigma transitions in low magnetic fields, 2mu ogB/(2N+l). These measurements are required in the data analysis of an ultra-sensitive (pptv) in situ detector based on magnetic-rotation spectroscopy.

Mahon, C. H.↗

Temperature Dependence of Nitrogen Broadening of the NO Fundamental Vibrational Band

We report measured N2-broadening coefficients, gamma (T), of approximately 70 transitions of the ground electronic state fundamental vibration-rotation band (v=1 (left arrow) 0) of NO at 183, 213 and 296K. In addition to the broadening asymmetry previously observed between the 2 pi 3/2 and 2 pi 1/2 state transitions, we also observed for most of the 2 pi 1/2 transitions an increased broadening of the f-lambda over e-lambda components. The temperature dependence of the broadening coefficients was characterized by the power law, gamma T = gamma 296 (296/T) (sup n).

Spencer, M. N.↗

The No Vibrational Fundamental Band: Temperature Dependence of N2- Broadening Coefficients

Rovibrational spectra of the vibrational fundamental of nitric oxide have been recorded under N2-broadening conditions using the Solar McMath FTS at the Kitt Peak National Observatory. The temperature range for the experiments was 296K to 183K. Qualitative as well as quantitative discrepancies are observed between these experimental determinations of the temperature dependence.

nitric oxide broadening coefficients vibrational f↗

Measurements of Band Intensities, Herman-Wallis Parameters, and Self-Broadening Line-Widths of the 30011 - 00001 and 30014 - 00001 Bands of CO2 at 6503 cm(exp -1) and 6076 cm(exp -1)

Rotationless band intensities and Herman-Wallis parameters are listed in HITRAN tabulations for several hundred CO2 overtone-combination bands. These parameters are based on laboratory measurements when available, and on DND calculations for the unmeasured bands. The DND calculations for the Fermi interacting nv(sub 1) + v(sub 3) polyads show the a(sub 2) Herman-Wallis parameter varying smoothly from a negative value for the first member of the polyad to a positive value for the final member. Measurements of the v(sub 1) + v(sub 3) dyad are consistent with the DND calculations for the a(sub 2) parameter, as are our recent measurements of the 4v(sub 1) + v(sub 3) pentad. However, the measurement-based values in the HITRAN tables for the 2v(sub 1) + v(sub 3) triad and the 3v(sub 1) + v(sub 3) tetrad do not support the DND calculated values for the a(sub 2) parameters. We therefore decided to make new measurements to improve some of these intensity parameters. With the McMath FTS at Kitt Peak National Observatory/National Solar Observatory we recorded several spectra of the. 4000 to 8000 cm(exp -1) region of pure CO2 at 0.011 cm(exp -1) resolution using the 6 meter White absorption cell. The signal/noise and absorbance of the first and fourth bands of the 3v(sub 1) + v(sub 3) tetrad of C-12O-16 were ideal on these spectra for measuring line intensities and broadening widths. Our selfbroadening results agree with the HITRAN parameterization, while our measurements of the rotationless band intensities are about 15% less than the HITRAN values. We find a negative value of a(sub 2) for the 30011-00001 band and a positive value for the 30014-00001 band, whereas the HITRAN values of a(sub 2) are positive for all four tetrad bands. Our a(sub 1) and a(sub 2) Herman-Wallis parameters are closer to DND calculated values than the 1992 HITRAN values for both the 30011-00001 and the 30014-00001 band.

Giver, L. P.↗

The Rovibrational Intensities of the (40 deg 1) and (00 deg 0) Pentad Absorption Bands of 12C16O2 Between 7284 and 7921 cm(exp-1)

Carbon dioxide is the major constituent of the atmospheres of both Mars and Venus. Correct interpretations of spectra of these atmospheres require accurate knowledge of a substantial number of absorption bands of this gas. This is especially true for Venus; many weak CO2 bands that are insignificant in the earth's atmosphere are prominent absorbers in Venus' hot, dense lower atmosphere. Yet, recent near-infrared spectra of Venus' nightside have discovered emission windows, which occur between CO2 absorption bands, at 4040-4550 cm(exp-1), 5700-5900 cm(exp-1), and several smaller ones between 7500 and 9400 cm(exp-1). This radiation is due to thermal emission from Venus' lower atmosphere, diminished by scattering and absorption within the sulfuric acid clouds on its way to space. Simulations of these data with radiative transfer models can provide improved information on the abundances of a number of constituents of the lower atmosphere (e.g. H2O, CO, HDO, HCl, HF, and OCS) and the optical properties of the clouds, whose spatial variation modulates the brightness of the emissions. However, the accuracy of these retrievals has been limited by insufficient knowledge of the opacity of some of the gas species, including CO2, at the large pathlengths and high temperatures and pressures that exist on Venus. In particular, modeling the emission spectrum did not produce a good fit for the emission window centered at 7830 cm(exp-1). In an ongoing effort to assist analyses of these Venus spectra, we have been making laboratory intensity measurements of several weak bands of CO2 which are significant absorbers in these Venus emission windows. The CO2 bands that are prominent in the 7830 cm(exp-1) region belong to the vibrational sequence 4v1+v3 and associated hot bands. Only 2 of the 5 bands of this sequence have been previously measured. Modeling Venus' emission spectrum in the 7830 cm(exp-1) region had to rely on calculated intensity values for the weak ground state band at 7921 cm-1 and the associated hot bands. Since the calculated intensities of ground state bands are known to have significant uncertainties, we decided to measure this (40 deg 1)I (left arrow) (00 deg 0) band with the Ames 25 meter multiple reflection absorption cell and Fourier transform spectrometer. We also measured the (40 deg 1) (sub IV) (left arrow) (00 deg 0) band at 7460 cm(exp-1), which also had not been previously measured. These measurements are reported in this article, and we also give our reanalysis of the prior measurements of the (40 deg 1) (sub III) (left arrow) (00 deg 0) bands. These measurements provide the basis for improving calculated intensities for related hot bands as well as simulations of Venus' spectrum.

Giver, L. P.↗

The No Vibrational Fundamental Band: Temperature Dependence of N2-Broadening Coefficients

Rovibrational spectra of the vibrational fundamental of nitric oxide have been recorded under N2-broadening conditions at 0.0056 cm(exp-1) resolution using the Solar McMath FTS at the Kitt Peak National Observatory. The temperature range for the experiments was 296 K to 183 K. The 30 cm absorption cell used for the measurements is cooled with a helium compressor and can operate at temperatures down to 60 K; vibration isolation of the cell allows its use with high performance Fourier Transform Spectrometers. From these spectra, N2-broadened line widths have been determined thru m = 16.5. Qualitative as well as quantitative discrepancies are observed between our experimental determinations of the temperature dependence of the broadening and theoretical calculations.

Spencer, M. N.↗

Production of organic compounds in plasmas: A comparison among electric sparks, laser-induced plasmas and UV light

In order to study the production of organic compounds in plasmas (and shocks), various mixtures of N2, CH4, and H2, modeling the atmosphere of Titan, were exposed to discrete sparks, laser-induced plasmas (LIP) and ultraviolet light. The yields of HCN and simple hydrocarbons were measured and compared to those calculated from a simple quenched thermodynamic equilibrium model. The agreement between experiment and theory was fair for HCN and C2H2. However, the yields of C2H6 and other hydrocarbons were much higher than those predicted by the model. Our experiments suggest that photolysis by ultraviolet light from the plasma is an important process in the synthesis. This was confirmed by the photolysis of gas samples exposed to the light, but not to the plasma or shock waves. The results of these experiments demonstrate that, in addition to the well-known efficient synthesis of organic compounds in plasmas, the yields of saturated species, e.g., ethane, may be higher than predicted by theory and that LIP provide a convenient and clean way of simulating planetary lightning and impact plasmas in the laboratory.

Scattergood, T. W.↗

N2-broadening in the HCl vibrational fundamental - Temperature dependence between 160 and 296 K

Measurements were conducted of the N2-broadening coefficients in the vibrational fundamental line of HCl at 160, 182, 216, 255, and 296 K. It is found that the N2 broadening of rovibrational lines in the -6 to +6 range is well described by a simple power-law dependence on temperature. The temperature-interpolation of these results is noted to be in good agreement with previous low-temperature studies.

Chackerian, C., Jr.↗

Quantitative infrared spectroscopy of minor constituents of the Earth's atmosphere

We obtain quantitative laboratory spectroscopic measurements of molecular constituents which are of importance in understanding the health of the Earth's atmosphere, and, in particular, emphasize those species which are important for understanding stratospheric kinetics or are used for long term monitoring of the stratosphere. Our measurements provide: (1) line and band intensity values which are needed to establish limits of detectability for as yet unobserved species and to quantify the abundance of those species which are observed; (2) line-positions, -half widths and pressure induced shifts are all needed for remote sensing techniques, and (3) data on the above basic molecular parameters at temperatures and pressures appropriate for the real atmosphere.

Chackerian, C., Jr.↗

Triton - Do we see to the surface?

The quantity and physical state of methane and nitrogen in the atmosphere of Neptune's satellite Triton and on the surface are evaluated by means of new telescopic data and laboratory measurements of these volatiles. Methane ice is seen in some spectral regions, indicating that the atmosphere is sufficiently transparent to permit sunlight penetration to the surface. Some of the molecular nitrogen absorption occurs in the atmosphere, though some must occur in condensed nitrogen (liquid or solid) on Triton's surface, or in a thin cloud of condensed nitrogen. The Voyager spacecraft cameras should see the surface of Triton.

Cruikshank, D. P.↗