Search

Cyano-substituted polycyclic aromatic hydrocarbons (CN-PAHs) may contribute to the emission detected in the 7 - 9 $\mu$m (1430 - 1100 cm$^{-1}$) and 11 - 15 $\mu$m (900 - 670 cm$^{-1}$) regions of astronomical IR spectra. Anharmonic quantum chemical computations of 17 CN-PAH isomers for 4 small PAHs and Benzene reveal strong, broad absorption features across the entire 300 - 6200 cm$^{-1}$ (33 - 1.6 $\mu$m) frequency range. In particular, when a FWHM of 15 cm$^{-1}$ is applied, the composite CN-PAH spectrum is almost indistinguishable from the unsubstituted-PAH spectrum. At high resolution, however, the infrared absorption spectra reveal unique, identifiable features of CN-PAHs in the 700 - 950, 1100 - 1300, 2000 - 2500, and 3400 - 3600 cm$^{-1}$ ranges. The in-plane and out-of-plane CH bending vibrational frequencies of CN-PAHs are shifted when comparing isomers and to their unsubstituted counterparts, making their differentiation in mixed laboratory experiments possible. The overall aromatic CH stretch fundamental (2950 - 3200 cm$^{-1}$) and first overtone (5950 - 6200 cm$^{-1}$) regions are relatively unaffected by the cyano-substitution, with changes only to the breadth and intensity of the bands. Detailed spectroscopic data on the normal mode components of each state reported herein provide the means to directly assign future laboratory spectra and to guide direct IR observations of astronomical regions with, e.g., JWST., Comment: Submitted to ACS Earth and Space Chemistry

We present 5-20 micron spectral maps of the reflection nebula NGC2023 obtained with the Infrared Spectrograph SL and SH modes on board the Spitzer Space Telescope which reveal emission from polycyclic aromatic hydrocarbons (PAHs), C60, and H2 superposed on a dust continuum. We show that several PAH emission bands correlate with each other and exhibit distinct spatial distributions revealing a spatial sequence with distance from the illuminating star. We explore the distinct morphology of the 6.2, 7.7 and 8.6 micron PAH bands and find that at least two spatially distinct components contribute to the 7--9 micron PAH emission in NGC2023. We report that the PAH features behave independently of the underlying plateaus. We present spectra of compact oval PAHs ranging in size from C_66 to C_210, determined computationally using density functional theory, and investigate trends in the band positions and relative intensities as a function of PAH size, charge and geometry. Based on the NASA Ames PAH database, we discuss the 7--9 micron components in terms of band assignments and relative intensities. We assign the plateau emission to very small grains with possible contributions from PAH clusters and identify components in the 7--9 micron emission that likely originates in these structures. Based on the assignments and the observed spatial sequence, we discuss the photochemical evolution of the interstellar PAH family as they are more and more exposed to the radiation field of the central star in the evaporative flows associated with the PDRs in NGC2023., Comment: 42 pages, 25 figures, 2 animations, accepted for ApJ

We present 15-20 um spectral maps towards the reflection nebula NGC2023 obtained with the Infrared Spectrograph in short-wavelength, high-resolution mode on board the Spitzer Space Telescope. These spectra reveal emission from PAHs, C60, and H2 superposed on a dust continuum. These emission components exhibit distinct spatial distributions: with increasing distance from the illuminating star, we observe the PAH emission followed by the dust continuum emission and the H2 emission. The C60 emission is located closest to the illuminating star in the south while in the north, it seems to be associated with the H/H2 transition. Emission from PAHs and PAH-related species produce features at 15.8, 16.4, 17.4, and 17.8 um and the 15-18 um plateau. These different PAH features show distinct spatial distributions. The 15.8 um band and 15-18 um plateau correlate with the 11.2 um PAH band and with each other, and are attributed to large, neutral PAHs. Conversely, the 16.4 um feature correlates with the 12.7 um PAH band, suggesting that both arise from species that are favored by the same conditions that favor PAH cations. The PAH contribution to the 17.4 um band is displaced towards the illuminating star with respect to the 11.2 and 12.7 um emission and is assigned to doubly ionized PAHs and/or a subset of cationic PAHs. The spatial distribution of the 17.8 um band suggests it arises from both neutral and cationic PAHs. In contrast to their intensities, the profiles of the PAH bands and the 15-18 um plateau do not vary spatially. Consequently, we conclude that the carrier of the 15-18 um plateau is distinct from that of the PAH bands., Comment: 34 pages, 8 fig. To appear in ApJ (accepted)

This white paper is submitted to the Astronomy and Astrophysics 2010 Decadal Survey (Astro2010)1 Committee on the State of the Profession to emphasize the potential of the Stratospheric Observatory for Infrared Astronomy (SOFIA) to contribute to the training of instrumentalists and observers, and to related technology developments. This potential goes beyond the primary mission of SOFIA, which is to carry out unique, high priority astronomical research. SOFIA is a Boeing 747SP aircraft with a 2.5 meter telescope. It will enable astronomical observations anywhere, any time, and at most wavelengths between 0.3 microns and 1.6 mm not accessible from ground-based observatories. These attributes, accruing from the mobility and flight altitude of SOFIA, guarantee a wealth of scientific return. Its instrument teams (nine in the first generation) and guest investigators will do suborbital astronomy in a shirt-sleeve environment. The project will invest $10M per year in science instrument development over a lifetime of 20 years. This, frequent flight opportunities, and operation that enables rapid changes of science instruments and hands-on in-flight access to the instruments, assure a unique and extensive potential - both for training young instrumentalists and for encouraging and deploying nascent technologies. Novel instruments covering optical, infrared, and submillimeter bands can be developed for and tested on SOFIA by their developers (including apprentices) for their own observations and for those of guest observers, to validate technologies and maximize observational effectiveness., Comment: 10 pages, no figures, White Paper for Astro 2010 Survey Committee on State of the Profession

The mid-IR spectra of six large, irregular PAHs with formulae (C84H24 - C120H36) have been computed using Density Functional Theory (DFT). Trends in the dominant band positions and intensities are compared to those of large, compact PAHs as a function of geometry, size and charge. Irregular edge moieties that are common in terrestrial PAHs, such as bay regions and rings with quartet hydrogens, are shown to be uncommon in astronomical PAHs. As for all PAHs comprised solely of C and H reported to date, mid-IR emission from irregular PAHs fails to produce a strong CCstr band at 6.2 um, the position characteristic of the important, class A astronomical PAH spectra. Earlier studies showed inclusion of nitrogen within a PAH shifts this to 6.2 um for PAH cations. Here we show this band shifts to 6.3 um in nitrogenated PAH anions, close to the position of the CC stretch in class B astronomical PAH spectra. Thus nitrogenated PAHs may be important in all sources and the peak position of the CC stretch near 6.2 um appears to directly reflect the PAH cation to anion ratio. Large irregular PAHs exhibit features at 7.8 um but lack them near 8.6 um. Hence, the 7.7 um astronomical feature is produced by a mixture of small and large PAHs while the 8.6 um band can only be produced by large compact PAHs. As with the CCstr, the position and profile of these bands reflect the PAH cation to anion ratio., Comment: accepted by ApJ

The mid-infrared spectra of large PAHs ranging from C54H18 to C130H28 are determined computationally using Density Functional Theory. Trends in the band positions and intensities as a function of PAH size, charge and geometry are discussed. Regarding the 3.3, 6.3 and 11.2 micron bands similar conclusions hold as with small PAHs. This does not hold for the other features. The larger PAH cations and anions produce bands at 7.8 micron and, as PAH sizes increases, a band near 8.5 micron becomes prominent and shifts slightly to the red. In addition, the average anion peak falls slightly to the red of the average cation peak. The similarity in behavior of the 7.8 and 8.6 micron bands with the astronomical observations suggests that they arise from large, cationic and anionic PAHs, with the specific peak position and profile reflecting the PAH cation to anion concentration ratio and relative intensities of PAH size. Hence, the broad astronomical 7.7 micron band is produced by a mixture of small and large PAH cations and anions, with small and large PAHs contributing more to the 7.6 and 7.8 micron component respectively. For the CH out-of-plane vibrations, the duo hydrogens couple with the solo vibrations and produce bands that fall at wavelengths slightly different than their counterparts in smaller PAHs. As a consequence, previously deduced PAH structures are altered in favor of more compact and symmetric forms. In addition, the overlap between the duo and trio bands may reproduce the blue-shaded 12.8 micron profile., Comment: ApJ, 36 pages, 9 figs

Over the past few decades, NASA missions have revealed that we live in a Universe that is not a hydrogen-dominated, physicist's paradise, but in a molecular Universe with complex molecules directly interwoven into its fabric. These missions have shown that molecules are an abundant and important component of astronomical objects at all stages of their evolution and that they play a key role in many processes that dominate the structure and evolution of galaxies. Closer to home in our galaxy, the Milky Way, they have revealed a unique and complex organic inventory of regions of star and planet formation that may well represent some of the prebiotic roots to life. Astrobiology emerges from the great interest in understanding astrochemical evolution from simple to complex molecules, especially those with biogenic potential and the roles they may play as primordial seeds in the origin of life on habitable worlds. The first part of this talk will highlight how infrared spectroscopic studies of interstellar space, combined with dedicated laboratory simulations, have revealed the widespread presence of complex organics across deep space. The remainder of the presentation will focus on the evolution of these materials and astrobiology.

Great strides have been made in our understanding of interstellar material thanks to advances in infrared astronomy and laboratory astrophysics. Ionized polycyclic aromatic hydrocarbons (PAHs), shockingly large molecules by earlier astrochemical standards, are widespread and very abundant throughout much of the cosmos. In cold molecular clouds, the birthplace of planets and stars, interstellar atoms and molecules freeze onto extremely cold dust and ice particles forming mixed molecular ices dominated by simple species such as water, methanol, ammonia, and carbon monoxide. Within these clouds, and especially in the vicinity of star and planet forming regions, these ices and PAHs are processed by ultraviolet light and cosmic rays forming hundreds of far more complex species, some of biogenic interest. Eventually, these are delivered to primordial planets by comets and meteorites. As these materials are the building blocks of comets and related to carbonaceous micrometeorites, they are likely to be important sources of complex organic materials delivered to habitable planets (including the primordial Earth) and their composition may be related to the origin of life. This talk will focus on the chemical evolution of these cosmic materials and their relevance to astrobiology.

Over 25 years of observations and laboratory work have shown that the mid-IR spectra of a majority of astronomical sources are dominated by emission features near 3.3, 6.2, 7.7, and 11.2 microns, which originate in free polycyclic aromatic hydrocarbon (PAH) molecules. PAHs dominate the mid-IR emission from many galactic and extragalactic objects. As such, this material tracks a wide variety of astronomical processes, making this spectrum a powerful probe of the cosmos Apart from bands in the mid-IR, PAHs have bands spanning the Far-IR (FIR) and emission from these FIR features should be present in astronomical sources showing the Mid-IR PAH bands. However, with one exception, the FIR spectral characteristics are known only for a few neutral small PAHs trapped in salt pellets or oils at room temperature, data which is not relevant to astrophysics. Furthermore, since most emitting PAHs responsible for the mid-IR astronomical features are ionized, the absence of any experimental or theoretical PAH ion FIR spectra will make it impossible to correctly interpret the FIR data from these objects. In view of the upcoming Herschel space telescope mission and SOFIA's FIR airborne instrumentation, which will pioneer the FIR region, it is now urgent to obtain PAH FIR spectra. This talk will present an overview recent advances in the laboratory spectroscopy of PAHs, Highlighting the FIR spectroscopy along with some quantum calculations.

Great strides have been made in our understanding of interstellar material thanks to advances in infrared astronomy and laboratory astrophysics. Ionized polycyclic aromatic hydrocarbons (PAHs), shockingly large molecules by earlier astrochemical standards, are widespread and very abundant throughout much of the Universe. In cold molecular clouds, the birthplace of planets and stars, interstellar molecules freeze onto dust and ice particles forming mixed molecular ices dominated by simple species such as water, methanol, ammonia, and carbon monoxide. Within these clouds, and especially in the vicinity of star and planet forming regions, these ices and PAHs are processed by ultraviolet light and cosmic rays forming hundreds of far more complex species, some of biogenic interest. Eventually, these are delivered to primordial planets by comets and meteorites. Astrochemical evolution, highlights of this field from a chemist's perspective, and the astronomer's infrared toolbox will be reviewed.

The composition of interstellar ice and dust provides insight into the chemical history of the interstellar medium and early solar system. It is now possible to probe this unique and unusual chemistry and determine the composition of these microscopic interstellar particles which are hundreds to many thousands of light years away thanks to substantial progress in two areas: astronomical spectroscopic techniques in the middle-infrared, the spectral region most diagnostic of chemical 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 giant, dark molecular clouds -the birthplace of stars and planets- and others in more tenuous, UV radiation rich regions are now available. The fundamentals of IR spectroscopy and what comparisons of astronomical IR spectra with laboratory spectra of materials prepared under realistic simulated interstellar conditions tell us about the components of these materials is the subject of this talk. These observations have shown that mixed molecular ices comprised of H2O, CH3OH, CO, NH3 and H2CO contain most of the molecular material in molecular clouds and that gas phase, ionized polycyclic aromatic hydrocarbons (PAHs) are widespread and surprisingly abundant throughout most of the interstellar medium.

Tremendous strides have been made in our understanding of interstellar material over the past twenty-five years thanks to significant developments in observational IR astronomy and dedicated laboratory experiments. Twenty-five years ago the composition of interstellar dust was largely guessed at. Today the composition of interstellar dust is reasonably well understood. In the diffuse interstellar medium (ISM) the dust population is mainly comprised of small grains of silicates and amorphous carbon. In dark molecular clouds, the birthplace of stars and planets, these cold refractory dust particles are coated with mixed molecular ices whose composition is reasonably well constrained. Lastly, the signature of carbon-rich polycyclic aromatic hydrocarbons (PAHs), shockingly large molecules by early interstellar chemistry standards, is widespread throughout the Universe. This extraordinary progress has been made possible by the close collaboration of laboratory experimentalists and theoreticians with IR astronomers using groundbased, air-borne, and orbiting telescopes.

In studying various interstellar and solar system ice analogs, we have recently found that upon vacuum ultraviolet photolysis, polycyclic aromatic hydrocarbons (PAHs) frozen in water ice at low temperatures are easily ionized and indefinitely stabilized as trapped ions (Gudipati; Gudipati & Allamandola). Here we report the first experimental study that shows that PAH ionization energy is significantly lowered in PAH/H2O ices, in agreement with recent theoretical work (Woon & Park). The ionization energy (IE) of the PAH studied here, quaterrylene (C40H20, IE = 6.11 eV), is lowered by up to 2.11 eV in water ice. PAH ionization energy reduction in low-temperature water ice substantially expands the astronomical regions in which trapped ions and electrons may be important. This reduction in ionization energy should also hold for other types of trapped species in waterrich interstellar, circumstellar, and solar system ices. Subject headings: ISM: clouds - methods: laboratory - molecular processes - radiation mechanisms: nonthermal -ultraviolet: ISM - ultraviolet: solar system

Organic compounds are synthesized in the interstellar medium and can be delivered to planetary surfaces such as the early Earth, where they mix with endogenous organic mixtures. Some of these compounds are amphiphilic, having polar and non-polar groups on the same molecule. Amphiphilic compounds spontaneously self-assembly into more complex structures such as bimolecular layers, which in turn form closed membranous vesicles. The first forms of cellular life required self-assembled membranes that were likely to be available on the prebiotic Earth. Laboratory simulations show that such vesicles readily encapsulate functional macromolecules, including nucleic acids and polymerases. A goal of future investigations is to fabricate artificial cells as models of the origin of life.

If we find evidence of Life elsewhere in the Solar System it will probably be in form of chemical biomarkers, quintessentially biological molecules that indicate the presence of micro-organisms. While molecules such as amino acids and nucleo-bases might seem to be biomarkers, and alkyl substituted aromatics have been invoked as such, they are not necessarily. These molecules are present in some meteorites and are expected to be present on the surface of other planets even in the absence of life. Understanding the range of non-biological organic molecules which could act as false biomarkers in space is a prerequisite for any reasonable search for true biomarkers on other worlds. Our experiments have shown that some organic molecules in meteorites that appear biological in nature are formed by energetic processing of extraterrestrial ices can account for amino acids, quinones and other functionalized aromatic compounds. In the past, such molecules have been proposed as biomarkers. For example, alkylated aromatics were invoked as biomarkers in the Alan Hills 84001 'Martian meteorite.' When simple organics arrive at the surface of a body like Europa, either from below or from space, how long do they survive and what do they make? How can we distinguish these from real biomarkers?

Polycyclic aromatic hydrocarbons (PAHs) are believed to be the most abundant and widespread class of organic compounds in the universe, having been observed in emission towards energetic regions and absorption towards colder ones.We will present IR spectra of PAHs and their cations in H20 ice measured in the laboratory in the hopes that this will facilitate the detection of these features in the interstellar medium.

Over the past fifteen years, thanks to significant, parallel advancements in observational, experimental, and theoretical techniques, tremendous strides have been made in our understanding of the role aromatic materials play in the interstellar medium (ISM). Twenty years ago, the possible existence of an abundant population of large, carbon-rich molecules in the ISM was unthinkable. Today, the unmistakable spectroscopic signatures of polycyclic aromatic hydrocarbon molecules (PAHs) - shockingly large molecules by the standards of traditional interstellar chemistry - are recognized throughout the Universe. In this paper, we will examine the current state of the interstellar PAH model and its utility as a diagnostic tool to derive insight into the nature of the interstellar PAH population. As an example of this application, we will examine the results of our recent spectroscopic studies of polycyclic aromatic nitrogen heterocycles (PANHs)-PAHs with an atom of nitrogen substituted into the aromatic skeleton-and discuss a possible tracer of such species amongst the interstellar PAH emission bands in the latest observational data.

In situ ultraviolet-visible absorption and emission studies of vacuum ultraviolet (VUV) irradiated water-rich, cosmic ice analogs containing polycyclic aromatic hydrocarbons (PAHs) are described. W V irradiation of 12 K water ices containing the PAHs naphthalene (H2O/C10H8 = 200) and 4-methylpyrene (H2O/C17H12 > 500) readily converts the PAHs into their cation form (PAH(+)). Under these conditions, PAH photoionization is the predominant reaction. These ions are trapped and stored in the ices at temperatures between 10 and 50 K, a temperature domain common to ices throughout interstellar clouds and the solar system. Unlike the approx.15% ionization typical after W V irradiation of PAHs isolated in rare-gas matrices, in water ice, PAH photoionization and storage proceed efficiently and almost quantitatively with a greater than 70% ionization yield. As the temperature is increased from 50 to 150 K, the PAH ion bands slowly diminish as the PAH ions ultimately react to form more complex organic species involving the water host. The chemical, spectroscopic, and physical properties of these ion-rich ices can be important in icy objects such as molecular clouds, comets, and planets. Several astrophysical applications are presented.

The NASA Astrobiology Roadmap provides guidance for research and technology development across the NASA enterprises that encompass the space, Earth, and biological sciences. The ongoing development of astrobiology roadmaps embodies the contributions of diverse scientists and technologists from government, universities, and private institutions. The Roadmap addresses three basic questions: How does life begin and evolve, does life exist elsewhere in the universe, and what is the future of life on Earth and beyond? Seven Science Goals outline the following key domains of investigation: understanding the nature and distribution of habitable environments in the universe, exploring for habitable environments and life in our own solar system, understanding the emergence of life, determining how early life on Earth interacted and evolved with its changing environment, understanding the evolutionary mechanisms and environmental limits of life, determining the principles that will shape life in the future, and recognizing signatures of life on other worlds and on early Earth. For each of these goals, Science Objectives outline more specific high-priority efforts for the next 3-5 years. These 18 objectives are being integrated with NASA strategic planning.

Here we report a study of the optical luminescent properties for a variety of vacuum-ultraviolet (VUV)- irradiated cosmic ice analogs and the complex organic residues produced. Detailed results are presented for the irradiated, mixed molecular ice: H2O:CH3OH:NH3:CO (100:50:1:1), a realistic representation for an interstellar/precometary ice that reproduces all the salient infrared spectral features associated with interstellar ices. The irradiated ices and the room-temperature residues resulting from this energetic processing have remarkable photoluminescent properties in the visible (520-570 nm). The luminescence dependence on temperature, thermal cycling, and VUV exposure is described. It is suggested that this type of luminescent behavior might be applicable to solar system and interstellar observations and processes for various astronomical objects with an ice heritage. Some examples include grain temperature determination and vaporization rates, nebula radiation balance, albedo values, color analysis, and biomarker identification.

Nitriles are one of the most common classes of molecules observed in the gas phase in space, with over a dozen having been positively identified in interstellar and circumstellar environments through the detection of their rotational transitions. Acids, in contrast, are much less common. In this paper we present laboratory data comparing the stability of two structurally related acid-nitrile pairs to ultraviolet (UV) photolytic destruction: acetic acid vs. acetonitrile (CH3-COOH vs. CH3-CN) and glycine vs. aminoacetonitrile (H2N-CH2-COOH vs. H2N-CH2-CN). We find that the nitriles are destroyed ten and five times more slowly (respectively) by UV photolysis than are the corresponding acids. This suggests that whatever their relative formation rates, acids may be less abundant than nitriles in interstellar environments in part because they are more rapidly destroyed by photolysis. The results of this infrared (IR) spectral matrix isolation study indicate that during the lifetime of a typical interstellar cloud, even in its darkest regions, a population of acids in the gas phase will likely be diminished by at least half. Since aminoacetonitrile is a precursor to the amino acid glycine, and far more stable, presolar aminoacetonitrile may be a contributor to the deuterium enriched glycine detected in meteorites. It would clearly be informative to search for aminoacetonitrile (the nitrile corresponding to glycine) in the regions where the amino acid glycine has been reported.

Water-rich, mixed molecular ices and polycyclic aromatic hydrocarbons (PAHs) are common throughout interstellar molecular clouds and the Solar System. Vacuum ultraviolet (VUV) irradiation and particle bombardment of these abiotic ices produces complex organic species, including important biogenic molecules such as amino acids and functionalized PAHs which may have played a role in the origin of life. This ability of such water-rich, oxygen dominated ices to promote production of complex organic species is surprising and points to an important, unusual, but previously overlooked mechanism at play within the ice. Here we report the nature of this mechanism using electronic spectroscopy. VUV-irradiation of PAH/H2O ices leads to an unprecedented and efficient (greater than 70 %) conversion of the neutral PAHs to their cation form (PAH+). Further, these H2O/PAH+ ices are stabile at temperatures below 50 K, a temperature domain common throughout interstellar clouds and the Solar System. Between 50 and 125 K they react to form the complex organics. In view of this, we conclude that charged PAHs and other molecular ions should be common and abundant in many cosmic ices. The chemical, spectroscopic and physical properties of these ion-rich ices can be of fundamental importance for objects as diverse as comets, planets, and molecular clouds and may account for several poorly understood phenomena associated with each of these object classes.

The cosmic deuterium to hydrogen (D/H) ratio is of key importance from a cosmological and stellar evolution perspective since deuterium originates from big-bang nucleosynthesis and is destroyed by stellar thermonuclear reactions. Further, from the interstellar perspective, the galactic distribution of deuterium and the D/H ratio among various molecular species also traces interstellar chemical evolution. Over the past few decades, radio observations have enabled the study of a handful of small, deuterated interstellar species. However, the number of deuterated species detected and environments probed are limited, raising issues of selection effects that hamper generalization and applications to other environments. Infrared spectroscopy of the interstellar medium offers a distinct advantage in this regard as the extent of deuteration of entire chemical families, rather than one species, can be probed. These observations require spaceborne telescopes because the molecular vibrations involving D which produce the strongest IR bands fall in spectral regions which are obscured by terrestrial CO2 absorption. Here we report the tentative detection of the C-D stretching vibration from deuterated interstellar polycyclic aromatic hydrocarbons in the Orion nebula. Since the PAH emission features are widespread and probe many different types of cosmic environments, follow up observations of deuterated PAHs will provide fundamental, far reaching new insight and perspective into galactic and extragalactic processes.

The delivery of extraterrestrial organic molecules to Earth by meteorites may have been important for the origin and early evolution of life. Indigenous amino acids have been found in meteorites-over 70 in the Murchison meteorite alone. Although it has been generally accepted that the meteoritic amino acids formed in liquid water on a parent body, the water in the Murchison meteorite is depleted in deuterium relative to the indigenous organic acids. Moreover, the meteoritical evidence for an excess of laevo-rotatory amino acids is hard to understand in the context of liquid-water reactions on meteorite parent bodies. Here we report a laboratory demonstration that glycine, alanine and serine naturally form from ultraviolet photolysis of the analogues of icy interstellar grains. Such amino acids would naturally have a deuterium excess similar to that seen in interstellar molecular clouds, and the formation process could also result in enantiomeric excesses if the incident radiation is circularly polarized. These results suggest that at least some meteoritic amino acids are the result of interstellar photochemistry, rather than formation in liquid water on an early Solar System body.

The gas-phase electronic absorption spectra of the naphthalene (C10H8(+)) and acenaphthene (C12H10(+)) cations have been measured in the visible range in a free 10 jet planar expansion in an attempt to collect data in an astrophysically relevant environment. The direct absorption spectra of two out of four bands measured of the gas-phase cold naphthalene cation along with the gas-phase vibronic absorption spectrum of the cold acenaphthene cation are reported for the first time. The study has been carried out using the ultrasensitive and versatile technique of cavity ringdown spectroscopy (CRDS) coupled to a pulsed discharge slit nozzle (PDN). The new CRDS-PDN set up is described and its characteristics are evaluated. The direct-absorption spectra of the PAH ions are discussed and compared to the gas-phase and solid-phase data available in the literature. The analysis of the results show that cold, free flying PAH ions are generated in the argon discharge primarily through soft Penning ionization. This enables the intrinsic band profiles to be measured, a key requirement for astrophysical applications.

Ultraviolet photolysis of various ice mixtures at low temperature and pressure caused the addition of amino (-NH2), methyl (-CH3), methoxy (-OCH3), and cyano (-CN) functional groups to the polycyclic aromatic hydrocarbon (PAH) coronene (C22H12). The implications of these results for interstellar and meteoritic chemistry are discussed. Previously only simple PAH photo-oxidation had been reported. This work represents the first experimental evidence that ice photochemistry may have contributed to aromatics bearing carbon and nitrogen containing side groups that are detected in primitive meteorites and interplanetary dust particles. Furthermore, these results suggest a wider range of modified PAHs should be expected in interstellar lees and materials predating solar system formation.

The optical luminescent properties for a variety of vacuum-ultraviolet (VUV) irradiated cosmic ice analogs and the complex organic residues produced from irradiation might be applicable to Solar System and interstellar observations and processes for various astronomical objects with an ice heritage. Some examples include grain temperature determination and vaporization rates, nebula radiation balance, albedo values, color analysis, and biomarker identification. Detailed results are presented for the mixed molecular ice: H2O:CH3OH:NH3:CO (100:50:1:1), a realistic representation for an interstellar/precometary ice. The irradiated ices and the room-temperature residues resulting from this energetic processing have remarkable photoluminescent properties in the visible (520-570 nm). The luminescence dependence on temperature, thermal cycling, and VUV exposure of the residue is described.

Much of the volatiles in interstellar dense clouds exist in ices surrounding dust grains. Their low temperatures preclude most chemical reactions, but ionizing radiation can drive reactions that produce a suite of new species, many of which are complex organics. The Astrochemistry Lab at NASA-Ames studies the UV radiation processing of interstellar ice analogs to better identify the resulting products and establish links between interstellar chemistry, the organics in meteorites, and the origin of life on Earth. Once identified, the spectral properties of the products can be quantified to assist with the search for these species in space. Of particular interest are findings that UV irradiation of interstellar ice analogs produces molecules of importance in current living organisms, including quiriones, amphiphiles, and amino acids. Quinones play a variety of roles including electron transport and are used by all organisms. Studies show that quinones should be made wherever polycyclic aromatic hydrocarbons are irradiated in interstellar ices (Bernstein et al. 2001). Amphiphiles are also made when mixed molecular ices are irradiated. These amphiphiles self-assemble into membrane-walled vesicles when put in liquid water (Dworkin et al. 2001). Ice irradiation can also produce (Bernstein et al. 2002) and destroy amino acids (Ehrenfreund et al. 2001). Many of the same processes thought to make organics in space should yield products highly enriched in deuterium (D) (Sandford et al. 2001). The high D/H ratios in some interstellar species, and the knowledge that many of the organics in primitive meteorites are D-enriched, suggests that such linkages do exist. By using D as a tracer, we expect to learn more about the different chemical processes occurring in space and their relative importance in the production of different organic compounds and delivery to planetary surfaces.

Comets and carbonaceous micrometeorites may have been significant sources of organic compounds on the early Earth. Ices on grains in interstellar dense molecular clouds contain a variety of simple molecules as well as aromatic molecules of various sizes. While in these clouds the icy grains are processed by ultraviolet light and cosmic radiation which produces more complex organic molecules. We have run laboratory simulations to identify the types of molecules which could have been generated photolytically in pre-cometary ices. Experiments were conducted by forming various realistic interstellar mixed-molecular ices with and without polycyclic aromatic hydrocarbons (PAHs) at approx. 10 K under high vacuum irradiated with UV light from a hydrogen plasma lamp. The residue that remained after warming to room temperature was analyzed by HPLC, and by laser desorption mass spectrometry. The residue contains several classes of compounds which may be of prebiotic significance.

Density functional theory has been employed to calculate the harmonic frequencies and intensities of a range of polycyclic aromatic hydrocarbon (PAH) cations that explore both size and electronic structure effects of the infrared spectroscopic properties of these species. The sample extends the size range of PAH species considered to more than 50 carbon atoms and includes several representatives from each of two heretofore unexplored categories of PAH cations: (1) fully benzenoid PAH cations whose carbon skeleton is composed of an odd number of carbon atoms (C(sub odd) PAHs); and (2) protonated PAH cations (HPAH+). Unlike the radical electronic structures of the PAH cations that have been the subject of previous theoretical and experimental work, the species in these two classes have a closed-shell electronic configuration. The calculated spectra of circumcoronene, C54H18 in both neutral and (radical) cationic form are also reported and compared with those of the other species. Overall, the C(sub odd) PAHs spectra are dominated by strong CC stretching modes near 1600 cm(exp -1) and display spectra that are remarkably insensitive to molecular size. The HPAH+ species evince a more complex spectrum consistent with the added contributions of aliphatic modes and their generally lower symmetry. Finally, for both classes of closed-shell cations, the intensity of the aromatic CH stretching modes is found to increase with molecular size far out of proportion with the number of CH groups, approaching a value more typical of neutral PAHs for the largest species studied.

Small biologically relevant organic molecules including the amino acids glycine, alanine, and marine were formed in the laboratory by the UV (Ultraviolet) photolysis of realistic interstellar ice analogs, composed primarily of H2O, and including CH3OH, NH3, and HCN, under interstellar conditions. N-formyl glycine, cycloserine (4-amino-3-isoxazolidinone), and glycerol were detected before hydrolysis, and glycine, racemic alanine, racemic marine, glycerol, ethanolamine, and glyceric acid were found after hydrolysis. This suggests that some meteoritic amino acids (and other molecules) may be the direct result of interstellar ice photochemistry, expanding the current paradigm that they formed by reactions in liquid water on meteorite parent bodies.

Interstellar gas and dust comprise the primary material from which the solar system formed. Evidence that some of this material was organic in nature and survived incorporation into the protosolar nebula is provided by the presence of deuterium-enriched organics in meteorites and interplanetary dust particles. Once the inner planets had sufficiently cooled, late accretionary infall of meteoroids and cosmic dust must have seeded them with some of these complex organic compounds. Delivery of such extraterrestrial compounds may have contributed to the organic inventory necessary for the origin of life. Interstellar ices, the building blocks of comets, tie up a large fraction of the biogenic elements available in molecular clouds. In our efforts to understand their synthesis, chemical composition, and physical properties, we report here that a complex mixture of molecules is produced by ultraviolet (UV) photolysis of realistic, interstellar ice analogs, and that some of the components have properties relevant to the origin of life, including the ability to self-assemble into vesicular structures.

Fluorescence spectra of the perylene cation, pumped by direct laser excitation via the D(sub 2)((2)B(sub 3g)) (left arrow) D(sub 0)((2)A(sub u)) and D(sub 5)(2)B(sub 3g)) (left arrow) D(sub 0)((2)A(sub u)) transitions, are presented. Direct excitation into the D5 or D2 states is followed by rapid non-radiative relaxation to D1 that, in turn,relaxes radiatively. Excitation spectroscopy across the D(sub 2)((2)B(sub 3g)) (left arrow) D(sub 0)((2)A(sub u)) transition near 730 nm shows that site splitting plays little or no role in determining the spectral substructure in the ion spectra. Tentative assignments for ground state vibrational frequencies are made by comparison of spectral intervals with calculated normal mode frequencies.

Infrared spectroscopy in the 2.5-16 micron range is a principle means by which organic compounds can be detected and identified in space via their vibrational transitions. Ground-based, airborne, and spaceborne IR spectral studies have already demonstrated that a significant fraction of the carbon in the interstellar medium (ISM) resides in the form of complex organic molecular species. Furthermore, the presence of D-enriched organics in meteorites suggests that a portion of these materials survives incorporation into protosolar nebulae. Unfortunately, neither the distribution of these materials nor their genetic and evolutionary relationships with each other or their environments are well understood. The Astrobiology Explorer (ABE) is a MIDEX mission concept currently under study at NASA's Ames Research Center in collaboration with Ball Aerospace and Technologies Corporation. ABE will conduct IR spectroscopic observations to address outstanding important problems in astrobiology, astrochemistry, and astrophysics. The core observational program would make fundamental scientific progress in understanding (1) the evolution of ices and organic matter in dense molecular clouds and young forming stellar systems, (2) the chemical evolution of organic molecules in the ISM as they transition from AGB outflows to planetary nebulae to the general diffuse ISM to HII regions and dense clouds, (3) the distribution of organics in the diffuse ISM, (4) the nature of organics in the Solar System (in comets, asteroids, satellites), and (5) the nature and distribution of organics in local galaxies. In addition, ABE will attempt to detect and quantify deuterium enrichments in a select set of these materials and environments. This should assist both with understanding the chemical processes that occur in these environments and with establishing any links that exist between interstellar and meteoritic organics.

One of the primary tasks of the Astrochemistry Laboratory at Ames Research Center is to use laboratory simulations to study the chemical processes that occur in dense interstellar clouds. Since new stars are formed in these clouds, their materials may be responsible for the delivery of organics to new habitable planets and may play important roles in the origin of life. These clouds are extremely cold (less than 50 kelvin), and most of the volatiles in these clouds are condensed onto dust grains as thin ice mantles. These ices are exposed to cosmic rays and ultraviolet (UV) photons that break chemical bonds and result in the production of complex molecules when the ices are warmed (as they would be when incorporated into a star-forming region). Using cryovacuum systems and UV lamps, this study simulates the conditions of these clouds and studies the resulting chemistry. Some of the areas of progress made in 1999 are described below. It shows some of the types of molecules that may be formed in the interstellar medium. Laboratory simulations have already confirmed that many of these compounds are made under these conditions.

The polycyclic aromatic hydrocarbon (PAH) naphthalene was exposed to ultraviolet radiation in H2O ice under astrophysical conditions, and the products were analyzed using infrared spectroscopy and high performance liquid chromatography. As we found in our earlier studies on the photoprocessing of coronene in H2O ice, aromatic alcohols and ketones (quinones) were formed. The regiochemistry of the reactions is described and leads to specific predictions of the relative abundances of various oxidized naphthalenes that should exist in meteorites if interstellar ice photochemistry influenced their aromatic inventory. Since oxidized PAHs are present in carbon-rich meteorites and interplanetary dust particles (IDPs), and ubiquitous in and fundamental to biochemistry, the delivery of such extraterrestrial molecules to the early Earth may have played a role in the origin and evolution of life.

We present 2338-2322 per centimeter (4.277-4.307 micrometer) infrared spectra of a number of N2-containing mixed molecular ices and demonstrate that the strength of the infrared "forbidden" band due to the N=N stretch near 2328 per centimeter (4.295 micrometer) is extremely sensitive to the composition of the ice. The strength of the 2328 per centimeter N2 fundamental is significantly enhanced relative to that of pure N2 ice when NH3, H2O, or CO2 are present, but is largely unaffected by the presence of CO, CH4 or O2. We use the laboratory data in coil junction with ISO data that probes several lines-of-sight through dense molecular clouds to place limits on the abundance of interstellar solid phase N2 and the composition of the ices. Deriving upper limits is complicated by the presence of overlapping absorptions due to CO2 gas in the clouds and, in some cases, to photospheric CO in the background star. These upper limits are just beginning to be low enough to constrain interstellar grain models and the composition of possible N2-bearing interstellar ices. We outline the search criteria that will need to be met if solid interstellar N2 is to be detected in the future. We also discuss some of the implications of the presence of warm CO2 gas along the lines-of-sight to embedded protostars and demonstrate that its presence may help resolve certain puzzles associated with the previously derived gas/solid CO2 ratios and the relative abundances of polar and nonpolar ices towards these objects. Finally, we briefly comment on the possible implications of these results for the interpretation of N2 detections on outer solar system bodies.

Density functional theory has been employed to calculate the harmonic frequencies and intensities of a range of PAH cations which explore both size and electronic structure effects on the infrared spectroscopic of these species. The sample extends the size range of PAH species considered to more than 50 carbon atoms and includes several representatives from each of two heretofore unexplored categories of PAH cations: (1) fully benzenoid PAH cations whose carbon skeleton is composed of an odd number of carbon atoms and (2) protonated PAH cations. Unlike the radical electronic structures of the PAH cations that have been the subject of previous theoretical and experimental work, the species in these two classes have a closed-shell electronic configuration. The calculated spectra of circumcoronene, C54H18, in both neutral and (radical) cationic form are also reported and compared to those of the other species. Closed-shell species are inherently less reactive than radical (or open-shell) cations and are known to play a role in combustion chemistry. Since interstellar PAHs are typically exposed to abundant atomic hydrogen and are thought to originate under pseudo-combustion conditions in carbon-rich circumstellar shells, such species may represent an important component of the interstellar PAH population. Furthermore, species larger than 50 carbon atoms are more representative of the size of the typical interstellar PAH. Overall, as has been the case for previous studies of PAH radical cations, the general pattern of band positions and intensities are consistent with that of the interstellar infrared emission spectrum. In addition, the spectra of closed-shell and open-shell cations are found to converge with increasing molecular size and are found to be relatively similar for species containing about 50 carbon atoms.

To better understand the chemical species that gives rise to the 2165/cm (4.62 micron) "XCN" absorption feature seen towards embedded protostars such as W33A, we have performed laboratory studies using deuterium (H-2) isotopic labeling. We report the observation of a small but significant deuterium isotope shift for the "XCN" peak which demonstrates that the atomic motion(s) causing the "XCN" band in the laboratory samples must involve hydrogen. We also report the results of C-13, N-15 and O-18 labeling experiments that are consistent with previously reported values.

Tremendous strides have been made in our understanding of interstellar material over the past twenty years thanks to significant, parallel developments in two closely related areas: observational astronomy and laboratory astrophysics. Twenty years ago the composition of interstellar dust was largely guessed at and the notion of abundant, gas phase, polycyclic aromatic hydrocarbons (PAHs) anywhere in the interstellar medium (ISM) considered impossible. Today the dust composition of the diffuse and dense ISM is reasonably well constrained and the spectroscopic case for interstellar PAHs, shockingly large molecules by early interstellar chemistry standards, is very strong.

Tremendous strides have been made in our understanding of interstellar material over the past twenty years thanks to significant, parallel developments in observational astronomy and laboratory astrophysics. Twenty years ago the composition of interstellar dust was largely guessed at, the concept of ices in dense molecular clouds ignored, and the notion of large, abundant, gas phase, carbon rich molecules widespread throughout the interstellar medium (ISM) considered impossible. Today the composition of dust in the diffuse ISM is reasonably well constrained to micron-sized cold refractory materials comprised of amorphous and crystalline silicates mixed with an amorphous carbonaceous material containing aromatic structural units and short, branched aliphatic chains. In dense molecular clouds, the birthplace of stars and planets, these cold dust particles are coated with mixed molecular ices whose composition is very well constrained. Lastly, the signature of carbon-rich polycyclic aromatic hydrocarbons (PAHs), shockingly large molecules by earlier interstellar chemistry standards, is widespread throughout the Universe. The first part of this lecture will describe how infrared studies of interstellar space, combined with laboratory simulations, have revealed the composition of interstellar ices (the building blocks of comets) and the high abundance and nature of interstellar PAHs. The laboratory database has now enabled us to gain insight into the identities, concentrations, and physical state of many interstellar materials. Within a dense molecular cloud, and especially in the solar nebula during the star and planet formation stage, the materials frozen into interstellar/precometary ices are photoprocessed by ultraviolet light, producing more complex molecules. The remainder of the presentation will focus on the photochemical evolution of these materials and the possible role of these compounds on the early Earth. As these materials are thought to be the building blocks of comets and related to the carbonaceous components of micrometeorites, they are likely to have been important sources of complex organic materials on the early Earth and their composition may be related to the origin of life.

We report here on our lab studies of ice photochemistry of large organic molecules under cometary conditions. We focus on polycyclic aromatic hydrocarbons (PAHs), their photoproducts, and their similarities to molecules seen in living systems today. We note that these kinds of compounds are seen in meteorites and we propose an explanation for both their formation and their observed deuterium enrichments.

There is a growing concensus among space scientists that frozen molecules from space helped to make the Earth the pleasant place that it is today, and helped Life start on Earth, and perhaps elsewhere. The chain of logic that led scientists to posit a connection between extraterrestrial molecules and the origin of life is as follows. 1) The rapidity with which life arose demands that conditions on Earth were conducive to the formation of life very early on. 2) There is reason to believe that comets and meteorites fell oil the Earth from its inception. 3) We now know that comets and meteorites are replete with complex organic compounds, some of which resemble those in living systems. 4) Perhaps the input of molecules from comets and meteorites provided crucial constituents to the primordial soup and Jump started life on Earth. 5) These molecules formed out in deep space long before the Earth ever existed, by processes that we can reproduce in the laboratory. 6) The fact that organic molecules are seen by astronomers throughout our galaxy and in others makes it seem likely that they were (and are) available to help start life in other planetary systems.

The Ames infrared spectral database of isolated, neutral and ionized polycyclic aromatic hydrocarbons (PAHs) shows that aromatic CH out-of-plane bending frequencies are significantly shifted upon ionization. For non-adjacent and doubly-adjacent CH groups, the shift is pronounced and consistently toward higher frequencies. The non-adjacent modes are blueshifted by an average of 27 per cm and the doubly-adjacent modes by an average of 17 per cm. For triply- and quadruply-adjacent CH out-of-plane modes the ionization shifts are more erratic and typically more modest. As a result of these ionization shifts, both the non-adjacent and doubly-adjacent CH out-of-plane modes move out of the regions classically associated with their respective vibrations in neutral PAHs. The doubly-adjacent modes of ionized PAHs tend to fall into the frequency range traditionally associated with the non-adjacent modes, while the non-adjacent modes are shifted to frequencies above those normally attributed to out-of-plane bending vibrations. Consequently, the origin of the interstellar infrared emission feature near 11.2 microns, traditionally attributed to the out-of-plane bending of non-adjacent CH groups on PAHs is rendered ambiguous. Instead, this feature likely reflects contributions from both non-adjacent CH units in neutral PAHs and doubly-adjacent CH units in PAH cations, the dominant charge state in the most energetic emission regions. This greatly relieves the structural constraints placed on the interstellar PAH population by the dominance of the 11.2 micron band in this region and eliminates the necessity to invoke extensive dehydrogenation of the emitting species. Furthermore, these results indicate that the emission between 926 and 904 per cm (10.8 and 11.1 microns) observed in many sources can be unambiguously attributed to the non-adjacent CH out-of-plane bending modes of moderately-sized (fewer than 50 carbon atom) PAH cations making this emission an unequivocal tracer of ionized interstellar PAHs.

The combination of realistic laboratory simulations and infrared observations have revolutionized our understanding of interstellar dust and ice-the main component of comets. Since comets and carbonaceous micrometeorites may have been important sources of volatiles and carbon compounds on the early Earth, their organic composition may be related to the origin of life. Ices on grains in molecular clouds contain a variety of simple molecules. The D/H ratios of the comets Hale-Bopp and Hyakutake are consistent with a primarily interstellar ice mixture. Within the cloud and especially in the presolar nebula through the early solar system, these icy grains would have been photoprocessed by the ultraviolet producing more complex species such as hexamethylenetetramine, polyoxymethylenes, and simple keones. We reported at the 1999 Bioastronomy meeting laboratory simulations studied to identify the types of molecules which could have been generated in pre-cometary ices. Experiments were conducted by forming a realistic interstellar mixed-molecular ice (H2O, CH3OH, NH3 and CO) at approximately 10 K under high vacuum irradiated with UV light from a hydrogen plasma lamp. The gas mixture was typically 100:50:1:1, however when different ratios were used material with similar characteristics was still produced. The residue that remained after warming to room temperature was analyzed by HPLC, and by several mass spectrometric methods. This material contains a rich mixture of complex compounds with mass spectral profiles resembling those found in IDPs and meteorites. Surface tension measurements show that an amphiphilic component is also present. These species do not appear in various controls or in unphotolyzed samples. Residues from the simulations were also dispersed in aqueous media for microscopy. The organic material forms 10-40 gm diameter droplets that fluoresce at 300-450 nm under UV excitation. These droplets have a morphology and internal structure which appear strikingly similar to those produced by extracts of the Murchison meteorite. Together, these results suggest a link between organic material photochemically synthesized on the cold grains in dense, interstellar molecular clouds and compounds that may have contributed to the organic inventory of the primitive Earth. For example, the amphiphilic properties of such compounds permit self-assembly into the membranous boundary structures that required for the first forms of cellular life.

The absorption spectra of pentacene (C22H14) and its radical cation (C22H14(+)) and anion (C22H14(-)) isolated in inert-gas matrices of Ne, Ar, and Kr are reported from the ultraviolet to the near-infrared. The associated vibronic band systems and their spectroscopic assignments are discussed together with the physical and chemical conditions governing ion (and counterion) production in the solid matrix. In particular, the formation of isolated pentacene anions is found to be optimized in matrices doped with alkali metal (Na and K).

The infrared spectra of six molecules, each of which contains a five-membered ring, and their cations are determined using density functional theory (DFT); both the B3LYP and BP86 functionals are used. The computed results are compared with the experimental spectra. For the neutral molecules, both methods are in good agreement with experiment. Even the Hartree-Fock (HF) approach is qualitatively correct for the neutrals. For the cations, the HF approach fails, as found for other organic ring systems. The B3LYP and BP86 approaches are in good mutual agreement for five of the six cation spectra, and in good agreement with experiment for four of the five cations where the experimental spectra are available. It is only for the fluoranthene cation, where the BP86 and B3LYP functionals yield different results; the BP86 yields the expected C2v symmetry, while the B3LYP approach breaks symmetry. The experimental spectra supports the BP86 spectra over the B3LYP, but the quality of the experimental spectra does not allow a critical evaluation of the accuracy of the BP86 approach for this difficult system.

Laboratory results demonstrate that polycyclic aromatic hydrocarbons (PAHs) rapidly exchange their hydrogen atoms with those of nearby molecules when they are frozen into low-temperature ices and exposed to vacuum ultraviolet radiation. As a result, PAHs quickly become deuterium-enriched when VUV irradiated in D-containing ices. This mechanism has important consequences for several astrophysical issues owing to the ubiquitous nature of PAHs in the interstellar medium. For example, this process may explain the deuterium enrichments found in PAHs in meteorites and interplanetary dust particles. These results also provide general predictions about the molecular siting of the deuterium on aromatic materials in meteorites if this process produced a significant fraction of their D-enrichment.

The so-called Unidentified Infrared or simply UIR bands, the infrared emission band spectrum associated with a wide variety of interstellar objects, can be modeled in detail by laboratory spectra of neutral and positively charged polycyclic aromatic hydrocarbon (PAH) mixtures. Fits are presented for the UIR emission from the protoplanetary nebula IRAS 22272+5435, the diffuse galactic medium, and the Orion HII/photodissociation front - a selection of objects which span the evolutionary range of interstellar material. These data directly address the spectroscopic criticisms previously leveled at the PAH hypothesis and demonstrate that PAH-related molecular species are indeed responsible for this widespread emission. Furthermore, these fits reflect the structure, abundance, and ionization state of the interstellar PAHs and, in turn, provide direct insight into the processes of carbon nucleation, growth and evolution in circumstellar shells and the interstellar medium. To date, no other candidate material which has been proposed to account for the UIR emission can as readily and specifically reproduce these spectral variations. Given the ubiquity of these species, this work demonstrates the tremendous potential of these species as probes of a new and heretofore largely unexplored facet of astrochemistry - potential which should make PAHs the probe of the next millennium much as CO has been for the last quarter century.

Calculations are carried out using density functional theory (DFT) to determine the harmonic frequencies and intensities of 1-methylanthracene, 9-methylanthracene, 9-cyanoanthracene, 2-aminoanthracene, acridine, and their positive ions. The theoretical data are compared with matrix-isolation spectra for these species also reported in this work. The theoretical and experimental frequencies and relative intensities for the neutral species are in generally good agreement, whereas the positive ion spectra are only in qualitative agreement. Relative to anthracene, we find that substitution of amethyl or CN for a hydrogen does not significantly affect the spectrum other than to add the characteristic methyl C-H stretch and C-N stretch (near 2200/cm), respectively. However, addition of NH2 dramatically affects the spectrum of the neutral. Not only are the NH2 modes themselves strong, but this electron withdrawing group induces sufficient partial charge on the ring to give the neutral molecule characteristics of the anthracene cation spectrum. The sum of the absolute intensities is about four times larger for 2-aminoanthracene than for 9-cyanoanthracene. Substituting nitrogen in the ring at the nine position (acridine) does not greatly alter the spectrum compared with anthracene.