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At least 181 records · Page 10

Experimental and Theoretical Studies of Interstellar Grains

Steady state vibrational populations of SiO and CO in dilute black body radiation fields were calculated as a function of total pressure, kinetic temperature and chemical composition of the gas. Approximate calculations for polyatomic molecules are presented. Vibrational disequilibrium becomes increasingly significant as total pressure and radiation density decrease. Many regions of postulated grain formation are found to be far from thermal equilibrium before the onset of nucleation. Calculations based upon classical nucleation theory or equilibrium thermodynamics are expected to be of dubious value in such regions. Laboratory measurements of the extinction of small iron and magnetite grains were made from 195 nm to 830 nm and found to be consistent with predictions based upon published optical constants. This implies that small iron particles are not responsible for the 220 nm interstellar extinction features. Additional measurements are discussed.

Nuth, J. A., III↗

The photochemistry of carbon-rich circumstellar shells

The effect of ambient ultraviolet photons on the chemical structure of carbon-rich, circumstellar envelopes is investigated with a simple formulation of the time-dependent, photochemical rate equations valid for optically thick shells. Molecules injected into the shielded inner envelope are broken down when they reach the outer regions where ambient ultraviolet photons can penetrate. A quantitative description of the abundance variations is obtained for the case of uniform expansion by detailed consideration of the shielding of the radiation by the dust and molecules of the envelope. Representative results are presented to illustrate the role of shielding in defining the extent of molecular envelopes, the formation of C I and C II shells by photodestruction of carbon-bearing molecules, and the development of layered chemical structures from the photobreakup of polyatomic molecules. Photochemistry makes the outer parts of thick, carbon-rich envelopes into complex regions containing radicals, ions, and atoms which are of considerable observational and theoretical interest.

Huggins, P. J.↗

Collisional narrowing in the optically pumped CH3OH and CH3F lasers

The gain linewidth of the optically pumped CH3F laser is observed to narrow and rebroaden with the addition of He. In addition, the same effect is observed in the CH3OH laser with the addition of the polyatomic buffer gases SF6 and CS2. These results offer conclusive evidence of the Dicke narrowing phenomena in these inverted pure rotational transitions. The effect is observed using a high harmonic mixing technique in a Schottky barrier diode.

Lawandy, N. M.↗

Heats of formation and thermodynamic functions for C2H, C3H, and C4H from 300 K to 6000 K

A review of the energy level and heat of formation data for the species C2H, C3H, and C4H is given. The procedure for computing thermochemical data from partition function is also reviewed. Working expressions for approximate partition functions, free-energy function, enthalpy function, and heat capacity for a linear polyatomic species are presented.

Saturno, A. F.↗

Theoretical studies of photodissociation of small molecules of astrophysical importance

The radicals and ions observed in comets result from photodissociation and photoionization of molecules. According to current models, a comet is composed chiefly of a large, solid nucelus of frozen gases (parent molecules) such as H2O, HCN, and NH3. It is believed comets were formed at the same time and in the same region of space as the major planets and that their chemical composition is the same as that of the early solar system. As the comet nears the Sun, the surface heats up, liberating the frozen gases as well as dust particles. Solar radiation photodissociates the parent molecules into fragments that are observed by resonance fluorescence. Both polyatomic molecules, present in the interstellar medium, and cometary radicals were observed. Using laboratory photo-dissociation data and computer models, astronomers are attempting to identify the parent molecules that account for all observed radicals and ions.

Saxon, R. P.↗

Test of Sigmund scaling for low collision energies

A scaling law that describes the most probable vibrorotational excitation in ion-molecule collisions has recently been extended by Sigmund (1981) to cover polyatomic targets. The predictions of this scaling law are examined for collisions of Cl(-) and K(+) with the targets O2, N2, CO, CO2, and CH4 in the energy range 50-200 eV. The experimental results do not all scale according to the theory. The study does demonstrate the usefulness of the scaling variables when examining the most probable vibrorotational excitation in ion-molecule collisions. A collection of isoelectronic scattering results is presented.

Vedder, M.↗

Low temperature operation of an S2 laser using radio frequency simmer discharges

Technological problems stemming from high temperature operation of the sulfur resonator have hindered its development as a tunable, efficient, discharge pumped laser. The use of RF simmer discharges is shown to reduce previous temperature constraints by dissociating polyatomic sulfur molecules into the dimer, such that lasing is achieved when pumped by an XeCl excimer laser. The peak power output of the S2 laser and the transmission spectra through sulfur discharges are used to infer the effectiveness of the discharge in dissociating the vapor.

Killeen, K. P.↗

Molecular orbital predictions of the vibrational frequencies of some molecular ions

The initial detections of IR vibration-rotation bands in polyatomic molecular ions by recent spectroscopic advances were guided by ab initio prediction of vibrational frequencies. The present calculations predict the vibrational frequencies of additional ions which are candidates for laboratory analysis. Neutral molecule vibrational frequencies were computed at three levels of theory and then compared with experimental data; the effect of scaling was also investigated, in order to determine how accurately vibrational frequencies could be predicted. For 92 percent of the frequencies examined, the relatively simple HF/6-31G theory's vibrational frequencies were within 100/cm of experimental values, with a mean absolute error of 49/cm. On this basis, the frequencies of 30 molecular ions (many possessing astrophysical significance) were computed.

Defrees, D. J.↗

Multi-level study of C3H2: The first interstellar hydrocarbon ring

Cyclic species in the interstellar medium have been searched for almost since the first detection of interstellar polyatomic molecules. Eleven different C3H2 rotational transitions were detected; 9 of which were studied in TMC-1, a nearby dark dust cloud, are shown. The 1 sub 10 yields 1 sub 01 and 2 sub 20 yields 2 sub 11 transitions were observed with the 43 m NRAO telescope, while the remaining transitions were detected with the 14 m antenna of the Five College Radio Observatory (FCRAO). The lines detected in TMC-1 have energies above the ground state ranging from 0.9 to 17.1 K and consist of both ortho and para species. Limited maps were made along the ridge for several of the transitions. The HC3N J = 2 yields 1 transition were mapped simultaneously with the C3H2 1 sub 10 yields 1 sub 01 line and therefore can compare the distribution of this ring with a carbon chain in TMC-1. C3H2 is distributed along a narrow ridge with a SE - NW extension which is slightly more extended than the HC2N J = 2 yields 1. Gaussian fits gives a FWHP extension of 8'5 for C3H2 while HC3N has a FWHP of 7'. The data show variations of the two velocity components along the ridge as a function of transition. Most of the transitions show a peak at the position of strongest HC3N emission while the 2 sub 21 yields 2 sub 10 transition shows a peak at the NH3 position.

Madden, S. C.↗

Two-photon laser-induced fluorescence detection of OH

The TP-LIF OH sensor is based on the principle that a molecule having multiple energy states, all of which are bonding, can be pumped into the highest state with the resulting fluorescence being blue-shifted relative to all pumping wavelengths. In this way, one can successfully discriminate against virtually all noise sources in the system using long wavelength blocking filters in conjunction with solar-blind photomultiplier tubes. Thus, these systems tend to be signal limited rather than signal-to-noise limited as is true of the SP-LIF technique as well as other conventional analytical methods. The trick to achieving the above sampling scheme, with high efficiency, is in the use of high photon fluxes of short time duration. Obviously, the latter type of light source is fulfilled nicely by available pulsed lasers. From an operational point of view, however, this laser source needs to be tunable. The latter characteristic permits extremely high selectivity for the detection of a diatomic or simple polyatomic molecule by taking advantage of the high-resolution spectroscopic features of these type species.

Davis, D. D.↗

Ultrasensitive detection of atmospheric trace gases using frequency modulation spectroscopy

Frequency modulation (FM) spectroscopy is a new technique that promises to significantly extend the state-of-the-art in point detection of atmospheric trace gases. FM spectroscopy is essentially a balanced bridge optical heterodyne approach in which a small optical absorption or dispersion from an atomic or molecular species of interest generates an easily detected radio frequency (RF) signal. This signal can be monitored using standard RF signal processing techniques and is, in principle, limited only by the shot noise generated in the photodetector by the laser source employed. The use of very high modulation frequencies which exceed the spectral width of the probed absorption line distinguishes this technique from the well-known derivative spectroscopy which makes use of low (kHz) modulation frequencies. FM spectroscopy was recently extended to the 10 micron infrared (IR) spectral region where numerous polyatomic molecules exhibit characteristic vibrational-rotational bands. In conjunction with tunable semiconductor diode lasers, the quantum-noise-limited sensitivity of the technique should allow for the detection of absorptions as small as .00000001 in the IR spectral region. This sensitivity would allow for the detection of H2O2 at concentrations as low as 1 pptv with an integration time of 10 seconds.

Cooper, David E.↗

Carbon monoxide in cometary ice

Carbon monoxide has been positively identified by means of ultraviolet fluorescence in the Fourth Positive System in two comets, West (1976 VI) and Bradfield (1979 X). In both cases, the spatial distribution of the emission is consistent with the CO being a 'parent' molecule, present in the cometary ice, rather than a dissociation product of a polyatomic species such as CO2 or HCOH. However, the abundance of CO relative to that of H2O is more than an order of magnitude smaller for comet Bradfield than for comet West. Further data on CO are expected with the use of more sensitive ultraviolet instruments such as the ASTRO spectrographs which will observe P/Halley in March 1986.

Feldman, P. D.↗

Picosecond coherent anti-Stokes Raman scattering (CARS) study of vibrational dephasing of carbon disulfide and benzene in solution

The vibrational dephasing of the 656/cm mode (nu1, a1g) of CS2 and the 991/cm mode (nu2, a1g) of benzene have been studied as a function of concentration in mixtures with a number of solvents using a ps time-resolved CARS technique. This technique employs two tunable synchronously-pumped mode-locked dye lasers in a stimulated Raman pump, coherent anti-Stokes Raman probe time-resolved experiment. Results are obtained for CS2 in carbon tetrachloride, benzene, nitrobenzene, and ethanol and for benzene nu2 in CS2. The dephasing rates of CS2 nu1 increase on dilution with the polar solvents and decrease or remain constant on dilution with the nonpolar solvents. The CS2/benzene solutions show a contrasting behavior, with the CS2 nu1 dephasing rate being nearly independent of concentration whereas the benzene nu2 dephasing rate decreases on dilution. These results are compared to theoretical models for vibrational dephasing of polyatomic molecules in solution.

Perry, Joseph W.↗

Climate-chemical interactions and effects of changing atmospheric trace gases

The paper considers trace gas-climate effects including the greenhouse effect of polyatomic trace gases, the nature of the radiative-chemical interactions, and radiative-dynamical interactions in the stratosphere, and the role of these effects in governing stratospheric climate change. Special consideration is given to recent developments in the investigations of the role of oceans in governing the transient climate responses, and a time-dependent estimate of the potential trace gas warming from the preindustrial era to the early 21st century. The importance of interacting modeling and observational efforts is emphasized. One of the problems remaining on the observational front is the lack of certainty in current estimates of the rate of growth of CO, O3, and NOx; the primary challenge is the design of a strategy that will minimize the sampling errors.

Ramanathan, V.↗

The violet and ultraviolet opacity problem for carbon stars

The paper considers the longstanding problem of the 'violet opacity' in cool carbon stars by testing, through synthetic spectra, many new and previously suggested opacity sources, based on currently available model atmospheres for carbon stars and M giant stars. While several bound-free edges of neutral metals are important opacity sources, those of Na I at at 2413 A, Mg I at 2514 A, and particularly Ca I at 2940 A are especially significant. Collectively, thousands of atomic lines are important, and the enormous line of Mg I at 2852 A influences the spectrum well into the visible. The pseudocontinuum of C3 and the photoionization continuum of CH both play noticeable but secondary roles. Synthetic spectra form the carbon star models with and without polyatomic molecules fit nicely the collected observations of the well-observed carbon star TX Psc.

Johnson, Hollis R.↗

New emission features in the 11-13 micron region and their relationship to polycyclic aromatic hydrocarbons

Moderate-resolution spectra of NGC 7027, HD 44179, IRAS 2182+5050, and BD +30 deg 3639 are presented, showing that the 11.3-micron feature actually peaks at 11.22 microns. Evidence is found for new emission features near 11.9 and 12.7 microns, supporting an origin from PAHs. Also, the observed asymmetry of the 11.3-micron band is consistent with the anharmonicity expected in the C-H out-of-plane bending mode in PAHs. The analysis of the 11-13-micron emission suggests that the molecular structures of the most intensely emitting free PAHs vary between the high-excitation environment in NGC 7027 and the low-excitation but high-flux environment close to HD 44179. In addition, a series of regularly spaced features between 10 and 11 microns is detected in the spectrum of HD 44179, suggesting that a simple polyatomic hydride is present in the object's gas phase.

Witteborn, F. C.↗

Determination of molecular spectroscopic parameters and energy-transfer rates by double-resonance spectroscopy

The spectroscopy of small to medium-size polyatomic molecules can be extremely complex, especially in higher-lying overtone and combination vibrational levels. The high density of levels also complicates the understanding of inelastic collision processes, which is required to model energy transfer and collision broadening of spectral lines. Both of these problems can be addressed by double-resonance spectroscopy, i.e., time-resolved pump-probe measurements using microwave, infrared, near-infrared, and visible-wavelength sources. Information on excited-state spectroscopy, transition moments, inelastic energy transfer rates and propensity rules, and pressure-broadening parameters may be obtained from such experiments. Examples are given for several species of importance in planetary atmospheres, including ozone, silane, ethane, and ammonia.

Steinfeld, J. I.↗

Theoretical investigation of gas-surface interactions

A Dirac-Hartree-Fock code was developed for polyatomic molecules. The program uses integrals over symmetry-adapted real spherical harmonic Gaussian basis functions generated by a modification of the MOLECULE integrals program. A single Gaussian function is used for the nuclear charge distribution, to ensure proper boundary conditions at the nuclei. The Gaussian primitive functions are chosen to satisfy the kinetic balance condition. However, contracted functions which do not necessarily satisfy this condition may be used. The Fock matrix is constructed in the scalar basis and transformed to a jj-coupled 2-spinor basis before diagonalization. The program was tested against numerical results for atoms with a Gaussian nucleus and diatomic molecules with point nuclei. The energies converge on the numerical values as the basis set size is increased. Full use of molecular symmetry (restricted to D sub 2h and subgroups) is yet to be implemented.

Dyall, Kenneth G.↗