Engineering topics

Allamandola, L. J.

Publications and source records attributed to Allamandola, L. J..

At least 73 records · Page 4

NASA NTRS1994

Electronic absorption spectroscopy of matrix-isolated polycyclic aromatic hydrocarbon cations. II. The phenanthrene cation (C14H10+) and its 1-methyl derivative

The ultraviolet, visible, and near infrared absorption spectra of phenanthrene (C14H10), 1-methylphenanthrene [(CH3)C14H9], and their radical ions [C14H10+; (CH3)C14H9+], formed by vacuum-ultraviolet irradiation, were measured in neon matrices at 4.2 K. The associated vibronic band systems and their spectroscopic assignments are discussed. The oscillator strengths were calculated for the phenanthrene ion and found lower than the theoretical predictions. This study presents the first spectroscopic data for phenanthrene and its methyl derivative trapped in a neon matrix where the perturbation of the isolated species by its environment is minimum; a condition crucial to astrophysical applications.

NASA Discipline Exobiology↗

NASA NTRS1994

Is H2O present on Io? The detection of a new strong band near 3590/cm (2.79 microns)

A strong absorption band at 3590 +/- 20/cm (2.790 +/- 0.015 microns) has been discovered in the spectrum of Io using the Kuiper Airborne Observatory (KAO). The 2nu(sub 1) + nu(sub 3) combination mode of solid SO2 falls at this position. Since SO2 is abundant on Io it must contribute to the new band. However, a band due to H2O was predicted near this frequency in Io's spectrum based on laboratory experiments of H2O:SO2 mixed Io ice analogs which were used to assign the two weak, variable features at 3370 and 3170/cm (2.97 and 3.15 microns) to trace amounts of H2O frozen in solid SO2 on Io. The new band probably originates from both SO2 and H2O. Unfortunately, the spectral resolution of the data is insufficient to settle the issue of whether there are two resolvable components.

Salama, F.↗

NASA NTRS1994

The temporal evolution of the 4-14 micron spectrum of V1974 Cygni (Nova Cygni 1992)

We present 4-14 micron spectra of the ONeMg nova V1974 Cygni (Nova Cygni 1992) obtained during 1992 May on the NASA Kuiper Airborne Observatory (KAO) and from the NASA 1.52 m infrared telescope at Mount Lemmon, Arizona in 1992 October/November with the HIFOGS mid-infrared spectrometer. The spectra at both epochs showed continuum emission from thermal bremstrahlung (free-free radiation) with emission lines from hydrogen and (Ne II), (Ar III), and Ne VI). During May, approximately = 80 days after outburst, the dominant emission lines in the mid-infrared spectra were a blend of three lines (Pf-alpha, Hu-beta, H11-7) near 7.5 microns and (Ne II) at 12.8 microns. By October (approximately 160 days later), the hydrogen emission had virtually disappeared, the (Ne II) 12.8 micron line had weakened considerably, and a pronounced (Ne VI) emission line had appeared at 7.6 microns. This behavior confirms that V1974 Cyg is similar to the prototypical slow ONeMg 'neon nova', Nova QU Vulpeculae (1984 No. 2). The remarkable evolution of the spectrum suggests that the ionization conditions changed drastically between 1992 May and 1992 October. We find that the ejecta of V1974 Cyg were overabundant in neon with respect to silicon by a factor of approximately 10 relative to the solar photosphere. We present new model calculations of infrared sodium forbidden line emission from (Na III) 7.319 microns (Na IV) 9.039 microns, and (Na IV) 21.29 microns that can be compared with recent model predictions of sodium synthesis in ONeMg nova outbursts. We conclude that sodium abundances in ONeMg novae can be determined by observations of infrared coronal lines of sodium that are accssible to the Infrared Space Observatory (ISO) and instruments at the NASA Infrared Telescope Facility (IRTF).

Gehrz, R. D.↗

NASA NTRS1994

Interstellar Ice and Dust: The Feedstock of the Solar System

Studying the chemical and isotopic composition of interstellar ice and dust provides insight into the composition and chemical history of the solid bodies in the solar nebula and the nature of the material subsequently brought into the inner part of the solar system by comets and meteorites. It is now possible to probe the composition of these microscopic interstellar particles (some hundreds of light years away), thanks to substantial progress in two areas: astronomical spectroscopic techniques in the middle-infrared, the spectral region most diagnostic of composition; and laboratory simulations which realistically reproduce the critical conditions in various interstellar environments. High quality infrared spectra of many different astronomical sources, some associated with dark molecular clouds, and others in the diffuse interstellar medium (DISM) are now available. What comparisons of these spectra with laboratory spectra tell us about the complex organic components of these materials is the subject of this talk. Most interstellar material is concentrated in large molecular clouds where simple molecules are formed by gas phase and dust grain surface reactions. Gaseous species (except H2) striking the cold (10K) dust will stick, forming an icy grain mantle. This accretion, coupled with energetic particle bombardment and UV photolysis, will produce a complex chemical mixture containing volatile, non-volatile, and isotopically fractionated species. One can compare spectra of the diffuse and dense interstellar medium with the spectra of analogs produced in the laboratory under conditions which mimic those in these different environments. In this way one can determine the composition and abundances of the major constituents present and place general constraints on the types and relative abundances of organics coating the grains. Ices in dense clouds contain H2O, CH3OH, CO, perhaps some NH3 and H2CO, as well as nitriles and ketones or esters. There is some evidence that the later, more complex species, are also present on the grains in the DISM. The evidence for these materials, in addition to carbon rich materials such as amorphous carbon, microdiamonds, and polycyclic aromatic hydrocarbons will be reviewed and the possible connection with meteoritic organics will be discussed.

Allamandola, L. J.↗

NASA NTRS1994

The Origins of Polycyclic Aromatic Hydrocarbons: Are They Everywhere?

During the past 15 years considerable progress in observational techniques has been achieved in the middle-infrared region (5000-500 per centimeter, 2-20 micron), the region where most diagnostic molecular vibrations occur. Spectra of many different astronomical infrared sources, some deeply embedded in dark molecular clouds and others at their edges, are now available. These spectra provide a powerful probe, not only for the identification of interstellar molecules in both the gas and solid phases, but also of the physical and chemical conditions which prevail in these two very different domains. The two lectures will focus on the evidence that polycyclic aromatic hydrocarbons (PAHs) are an important, ubiquitous and abundant interstellar species. PAHs are. extremely stable species which can range in size from a few angstroms across to several hundred angstroms (PAHs are also the building blocks of amorphous carbon particles). This identification rests on the suggestive agreement between the laboratory spectra of PAHs with a set of IR emission bands which emanate from many different sources where ultraviolet starlight impinges on a "dusty" region. The picture is that individual PAHs are first pumped into highly vibrationally excited states and relax by fluorescence at their fundamental vibrational frequencies. That PAHs are a ubiquitous interstellar component has serious ramifications in other spectral regions as well, including the strong extinction in the ultraviolet, and the classic visible diffuse interstellar bands discovered more than 50 years ago (but unexplained to this day) The first part of the course will focus on the interpretation of astronomical spectra. The second lecture will start by showing how recent laboratory data on PAHs taken under realistic interstellar conditions has con borated the PAH hypothesis and led to great insight into the conditions in the PAH containing regions. This lecture will end by reviewing the ever-increasing evidence for interstellar PAHs in meteorites and interplanetary dust particles. This in conjunction with the recent suggestion that PAHs are abundant in Jupiter's atmosphere will make the point that "PAHs are Everywhere".

Allamandola, L. J.↗

NASA NTRS1994

Infrared Spectroscopy of Polycyclic Aromatic Hydrocarbon Cations: The Members - 3

In spite of the fact that the infrared spectroscopic properties of only a few isolated ionized polycyclic aromatic hydrocarbons (PAHs) are known, gaseous, ionized PAHs are thought to be responsible for a very common family of infrared interstellar emission bands. In order to provide a data base to test this hypothesis and, if borne out, to use this emission band family as a probe of many different interstellar environments, we are carrying out a thorough study of the infrared spectroscopic properties of neutral and ionized PAHs in argon matrices. Here we present the near and mid-infrared spectra of the cations of the five most thermodynamically favored PAHs up to coronene: phenanthrene, pyrene, benzo[e]pyrene, benzo[ghilperylene, and coronene. The properties of naphthalene, the first member of the series, are given elsewhere. The spectra of perdeuterated phenanthrene and pyrene are also reported. For those molecules which have been previously studied (pyrene, d(10)-pyrene, and coronene), band positions and relative intensities are in agreement. In all cases we report additional features. Absolute integrated absorbance values are given for the phenanthrene, perdeutero-phenanthrene, pyrene, benzo[ghi]perylene, and coronene cations. With the exception of coronene,the cation bands corresponding to the CC modes are typically 2-5 times more intense than those of the CH out-of-plane bending vibrations. For the cations the CC stretching and CH in-plane bending modes give rise to bands which are an order of magnitude stronger than for the neutral species, and the CH out-of-plane bends produce bands which are 5-20 times weaker than in the neutral species. This behavior is similar to that found in most other PAH cations studied to date. The astronomical implications of these PAH cation spectra are also discussed.

Hudgins, D. M.↗

NASA NTRS1993

Theoretical modeling of the infrared fluorescence from interstellar polycyclic aromatic hydrocarbons

We have modeled the family of interstellar IR emission bands at 3.3, 6.2, 7.7, 8.6, 11.3, and 12.7 microns by calculating the fluorescence from a size distribution of interstellar polycyclic aromatic hydrocarbons (PAHs) embedded in the radiation field of a hot star. It is found that the various emission bands are dominated by distinctly different PAHs, from molecules with much less than about 80 C atoms for the 3.3 micron feature, to molecules with 10 exp 2-10 exp 5 C atoms for the emission in the IRAS 12 and 25 micron bands. We quantitatively describe the influence on the emergent spectrum of various PAH properties such as the molecular structure, the amount of dehydrogenation, the intrinsic strength of the IR active modes, and the size distribution. Comparing our model results to the emission spectrum from the Orion Bar region, we conclude that interstellar PAHs are likely fully, or almost fully, hydrogenated. Moreover, it is found that the intrinsic strengths of the 6.2 and 7.7 micron C-C stretching modes, and the 8.6 micron C-H in-plane bending mode are 2-6 times larger than measured for neutral PAHs in the laboratory.

Schutte, W. A.↗

NASA NTRS1993

An experimental study of the organic molecules produced in cometary and interstellar ice analogs by thermal formaldehyde reactions

Results of an experimental study tracing thermal formaldehyde reactions in astrophysically relevant ices in dense molecular clouds are reported. The formaldehyde chemistry during warm-up of ices containing H2CO and one or more of the molecules H2O, CH3OH, CO, O2, and NH3 were monitored using IR spectroscopy. Conversion of H2CO into residues was observed to start at about 40 K for NH3:H2CO ices and at about 80 K in H2O-rich ices. A total of five different organic products of these reactions were distinguished: POM and reaction products of H2CO and H2O, CH3OH, and NH3. Given the measured reaction paths and efficiencies, it is estimated that on the order of 1 percent of the organics found in the coma of Comet P/Halley could have been produced by thermal formaldehyde reactions taking place in the nucleus.

Schutte, W. A.↗

NASA NTRS1993

Mid- and far-infrared spectroscopy of ices - Optical constants and integrated absorbances

Laboratory spectra through the mid-infrared (4000 to 500/cm (2.5-20 microns) have been used to calculate the optical constants (n and k) and integrated absorption coefficients (A) for a variety of pure and mixed molecular ices of relevance to astrophysics. The ices studied were H2O, CH3OH, CO2, OCS, CH4, CO2 + CH4, CO2 + OCS, CO + CH4, CO + OCS, O2 + CH4, O2 + OCS, N2 + CH4, N2 + OCS, H2O + CH4, H2O + OCS, and H2O + CH3OH + CO + NH3. In addition, the measurements have been extended through the far-infrared (500 to 50/cm (20-200 microns) for the H2O, CH3OH, and H2O + CH3OH + CO + NH3 ices.

Hudgins, D. M.↗

NASA NTRS1993

Diamonds in dense molecular clouds - A challenge to the standard interstellar medium paradigm

Observations of a newly discovered infrared C-H stretching band indicate that interstellar diamond-like material appears to be characteristic of dense clouds. In sharp contrast, the spectral signature of dust in the diffuse interstellar medium is dominated by -CH2- and -CH3 groups. This dichotomy in the aliphatic organic component between the dense and diffuse media challenges standard assumptions about the processes occurring in, and interactions between, these two media. The ubiquity of this interstellar diamond-like material rules out models for meteoritic diamond formation in unusual circumstellar environments and implies that the formation of the diamond-like material is associated with common interstellar processes or stellar types.

Allamandola, L. J.↗

NASA NTRS1993

Formaldehyde and organic molecule production in astrophysical ices at cryogenic temperatures

Thermally promoted formaldehyde (H2CO) reactions in cryogenic ices have been studied to test their importance as a source of organic molecules in comets and interstellar ices. Ices containing H2CO, H2O, CH3OH, CO, and NH3 were investigated by using infrared spectroscopy. Small traces of NH3 (NH3/H2CO equal to or greater than 0.005) are sufficient to convert significant fractions (40 percent or greater) of the H2CO into more complex organics. However, H2CO reactions do not proceed without NH3. Spectral evidence for reaction onset appeared between 40 and 80 K, depending on the ice. Five distinct products were formed. These principally consist of polyoxymethylene and related derivatives. Polyoxymethylene itself was not made in significant amounts in cometary analogs. These products differ from those produced by ultraviolet and particle irradiation. The nature and relative amounts of the products depend on the initial composition, making these materials excellent tracers of a comet's history. About 3 percent of the organics in p-Halley's coma could have been produced by thermal H2CO reactions.

Schutte, W. A.↗

NASA NTRS1992

Infrared spectroscopy of dense clouds in the C-H stretch region - Methanol and 'diamonds'

The paper presents high spectral resolution studies in the 3100-2600/cm range of the protostars NGC 7538 IRS9, W33A, W3 IRS 5, and S140 IRS 1. Well-resolved absorption bands at about 2825/cm and 2880/cm were found superposed on the LF wing of the strong O-H stretch feature. The 2880/cm band, previously detected toward W33A, is also in the spectrum of NGC 7538 IRS 9. The relative strength of these two bands varies, showing that they are associated with two different carriers. The new band at about 2880/cm falls near the position of C-H stretching vibrations in tertiary carbon atoms. The strength of this feature, in combination with the lack of strong features associated with primary and secondary carbon atoms, suggests that the carrier of the new feature has a diamondlike structure. This new feature is tentatively attributed to interstellar 'diamonds'. The detection of this band in the spectra of all four dense molecular clouds suggests that the carrier is ubiquitous in dense clouds.

Allamandola, L. J.↗

NASA NTRS1992

The ultraviolet and visible spectrum of the polycyclic aromatic hydrocarbon C10H8(+) - Possible contributions to the diffuse interstellar bands and to the ultraviolet-visible extinction

The properties of the cation of the PAH naphthalene (C10H8(+)) isolated in inert gas matrices under conditions relevant to astrophysical environments are described. The band at 6741 A is the strongest and falls close to the weak 6742 A diffuse interstellar bands (DIBs). Five other weaker bands also fall remarkably close to the positions of known DIBs. A very intense and broad continuum extended from the UV to the visible, which seems to be associated with the ion, is reported. The molar absorption coefficient at the peak of the continuum is 2.0 x 10 exp 6 cu dm/mol cm. If a continuum is a general property of PAH cations, this characteristic will have a strong impact on the understanding of how PAHs convert interstellar UV and visible radiation into IR radiation.

Salama, F.↗

NASA NTRS1992

Is a pyrene-like molecular ion the cause of the 4,430-A diffuse interstellar absorption band?

The diffuse interstellar band (DIB) absorption features of astronomical spectra are suggested by recent results to be separable from the grains that cause visual extinction. Attention is presently given to laboratory measurements of the optical spectrum of the pyrene cation C16H10(+), which is one of the polycyclic aromatic hydrocarbon (PAH) molecular candidates proposed as carriers for DIBs. This ion exhibits an intense but strangely broad continuum similar to that of the naphthalene cation, so that this may be a common feature of all PAH cations and the basis of an explanation for PAHs' converting of an interstellar radiation fraction as large as that from the UV and visible range down to the IR.

Salama, F.↗

NASA NTRS1992

Is a pyrene-like molecular ion the cause of the 4,430-angstroms diffuse interstellar absorption band?

The diffuse interstellar bands (DIBs), ubiquitous absorption features in astronomical spectra, have been known since early this century and now number more than a hundred. Ranging from 4,400 angstroms to the near infrared, they differ markedly in depth, width and shape, making the concept of a single carrier unlikely. Whether they are due to gas or grains is not settled, but recent results suggest that the DIB carriers are quite separate from the grains that cause visual extinction. Among molecular candidates the polycyclic aromatic hydrocarbons (PAHs) have been proposed as the possible carriers of some of the DIBs, and we present here laboratory measurements of the optical spectrum of the pyrene cation C16H10+ in neon and argon matrices. The strongest absorption feature falls at 4,435 +/- 5 angstroms in the argon matrix and 4,395 +/- 5 angstroms in the neon matrix, both close to the strong 4,430-angstroms DIB. If this or a related pyrene-like species is responsible for this particular band, it must account for 0.2% of all cosmic carbon. The ion also shows an intense but puzzling broad continuum, extending from the ultraviolet to the visible, similar to what is seen in the naphthalene cation and perhaps therefore a common feature of all PAH cations. This may provide an explanation of how PAHs convert a large fraction of interstellar radiation from ultraviolet and visible wavelengths down to the infrared.

NASA Center ARC↗

NASA NTRS1992

Laboratory simulation of the photoprocessing and warm-up of cometary and pre-cometary ices - Production and analysis of complex organic molecules

The recent missions to Comet Halley detected large quantities of organic material on grains as well as organic molecules in the gas phase. A possible origin of these materials is the energetic processing of ice mantles on the grains prior to comet formation, either in the pre-solar nebula or the interstellar medium. This process was simulated in the laboratory by depositing interstellar ice analogs (H2O/CH3OH/CO/NH3) on a cold (10 K) substrate with simultaneous UV irradiation. The material evaporating during warm-up of the photolyzed ice as well as the residue remaining at room temperature was analyzed by a number of techniques. It was found that a large number of organic molecules of various complexity are synthesized during the simulation process, stressing the possible significance of UV photolysis for producing the organic Comet material.

Schutte, W. A.↗

NASA NTRS1992

Grain Spectroscopy

Our fundamental knowledge of interstellar grain composition has grown substantially during the past two decades thanks to significant advances in two areas: astronomical infrared spectroscopy and laboratory astrophysics. The opening of the mid-infrared, the spectral range from 4000-400 cm(sup -1) (2.5-25 microns), to spectroscopic study has been critical to this progress because spectroscopy in this region reveals more about a materials molecular composition and structure than any other physical property. Infrared spectra which are diagnostic of interstellar grain composition fall into two categories: absorption spectra of the dense and diffuse interstellar media, and emission spectra from UV-Vis rich dusty regions. The former will be presented in some detail, with the latter only very briefly mentioned. This paper summarized what we have learned from these spectra and presents 'doorway' references into the literature. Detailed reviews of many aspects of interstellar dust are given.

Allamandola, L. J.↗

NASA NTRS1991

Solid C triple bond N bearing material on outer solar system bodies

Recent telescopic observations have led to the identification of cyanogroup-containing molecules in the dark surface solids of several D-class asteroids, cometary dusts, and the rings of Uranus, as well as the low-albedo atmosphere of Iapetus. The occurrence of the 2.2-micron overtone of C triple-bond N's stretching fundamental mode in all four classes of small solar system bodies is presently suggested to serve as a diagnostic of both exposure duration and degree of modification of surface materials.

Cruikshank, Dale P.↗