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D1((2)B2g) to D0((2)Au) Fluorescence from the Matrix-Isolated Perylene Cation Following Laser Excitation into the D5(2)B3g) and D2 ((2)B3g) Electronic States

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.

Chillier, Xavier D. F.↗

The Infrared Spectrum of Matrix-Isolated Hexamethylenetetramine in Argon at 12 K

It is commonly accepted that constant exposure of comets and ice grains to ultraviolet (UV) radiation causes an organic crust to form on their surface, but the exact molecules that comprise the crust remains a mystery. Based on our lab simulations of interstellar and cometary ices (a paper to be submitted this spring) we believe that Hexamethylenetetramine (HMT) may be a major component of the organic crust on the surface of comets and ice grains. The enclosed paper presents the laboratory infrared spectra and UV photochemistry of HMT under conditions akin to that of the interstellar medium.

Bernstein, Max P.↗

Infrared spectroscopy of matrix-isolated polycyclic aromatic hydrocarbon cations. 2. The members of the thermodynamically most favorable series through coronene

Gaseous, ionized polycyclic aromatic hydrocarbons (PAHs) are thought to be responsible for a very common family of interstellar infrared emission bands. Here 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[ghi]perylene, and coronene, are presented to test this hypothesis. For those molecules that have been studied previously (pyrene, pyrene-d10, and coronene), band positions and relative intensities are in agreement. In all of these cases we report additional features. Absolute integrated absorbance values are given for the phenanthrene, perdeuteriophenanthrene, 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 that are an order of magnitude stronger than those of the neutral species, and the CH out-of-plane bends produce bands that are 5-20 times weaker than those of 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.

NASA Discipline Exobiology↗

Investigation of a laboratory candidate for the carrier of the 4430 A diffuse interstellar band

The 4430 A diffuse interstellar band (DIB) is unique among DIB's in that as one of the strong bands, it is the bluest strong band with no others observed at shorter wavelengths. This position at the edge of the DIF 'forrest' suggests it may be the easiest to replicate in the laboratory. In earlier experiments (Wdowiak 1980) an interesting candidate using a gas discharge followed by cryogenic matrix isolation was produced, and this report details its further investigation. This absorption feature, produced when 1 part CH4 in 200 parts Ar is discharged and frozen out approximately 10 K, is at a wavelength of 4500 A in the argon matrix. Our recent experiments strongly indicate it is due to a carbon-based reactive species that is stable against mercury vapor UV radiation, and not likely to be from a contaminant. The effect of matrix shift can be estimated by considering the blueward shift between Ar and Ne matrices in the cases of the pyrene and C60 cations. This suggests that a shift from 4500 A for an Af matrix to the vicinity of 4300 A for a Ne matrix and the gas phase is not unreasonable. A liquid He cooled Ne matrix isolation experiment was prepared to determine the wavelength of the feature in that matrix. Replacing CH4 with C2H2 results in an equivalent absorption due to C3, greatly diminished absorptions from C2 and Ch, and no observable feature at 4500 A. To date our experiments indicate CH4 is a favored precursor for production of the reactive carrier of the 4500 A feature. Perhaps C2H2 is not suitable because of its tendency to polymerize easily in the discharge.

Wdowiak, Thomas J.↗

Experimental and Theoretical Study of Oxolan-3-one Thermal Decomposition

The thermal decomposition of oxolan-3-one, a common component of the bio-oil formed during biomass pyrolysis, has been studied using ab initio calculations and experiments employing pulsed gas-phase pyrolysis with matrix isolation FTIR product detection. Four pathways for unimolecular decomposition were predicted using computational methods. The dominant reaction channel led to carbon monoxide, formaldehyde, and ethylene, all of which were observed experimentally. Here, the other channels led to an assortment of products including ketene, water, propyne, and acetylene, which were all confirmed in the matrix-isolation FTIR spectra. There is also evidence for the production of substituted ketenes in pyrolysis, most likely hydroxyketene and methylketene.

09 BIOMASS FUELS↗

Theoretical Infrared Spectra for Polycyclic Aromatic Hydrocarbon Neutrals, Cations and Anions

Calculations are carried out using density functional theory (DFT) to determine the harmonic frequencies and intensities of the neutrals and cations of thirteen polycyclic aromatic hydrocarbons (PAHs) up to the size of ovalene. Calculations are also carried out for a few PAH anions. The DFT harmonic frequencies, when uniformly scaled by the factor of 0.958 to account primarily for anharmonicity, agree with the matrix isolation fundamentals to within an average error of about 10 per centimeter. Electron correlation is found to significantly reduce the intensities of many of the cation harmonics, bringing them into much better agreement with the available experimental data. While the theoretical infrared spectra agree well with the experimental data for the neutral systems and for many of the cations, there are notable discrepancies with the experimental matrix isolation data for some PAH cations that are difficult to explain in terms of limitations in the calculations. In agreement with previous theoretical work, the present calculations show that the relative intensities for the astronomical unidentified infrared (UIR) bands agree reasonably well with those for a distribution of polycyclic aromatic hydrocarbon (PAH) cations, but not with a distribution of PAH neutrals. We also observe that the infrared spectra of highly symmetrical cations such as coronene agree much better with astronomical observations than do those of, for example, the polyacenes such as tetracene and pentacene. The total integrated intensities for the neutral species are found to increase linearly with size, while the total integrated intensities are much larger for the cations and scale more nearly quadratically with size. We conclude that emission from moderate-sized highly symmetric PAH cations such as coronene and larger could account for the UIR bands.

Langhoff, Stephen R.↗

Laboratory Infrared Spectra of Polycyclic Aromatic Nitrogen Heterocycles: Quinoline, and Phenanthridine in Solid Argon and H2O

Polycyclic aromatic hydrocarbons (PAHs) are common throughout the universe. Their detection and identification are based on telescopic infrared (IR) spectra compared with laboratory data. Polycyclic Aromatic Nitrogen Heterocycles (PANHs) are heterocyclic aromatics i.e., PAHs with carbon atoms replaced by a nitrogen atom. These molecules should be present in the interstellar medium, but have received relatively little attention. We present mid-IR spectra of two PANHs, quinoline (C9H7N), and phenanthridine (C13H9N) isolated in solid argon and frozen in solid H2O at 12 K, conditions yielding data directly comparable to astronomical observations. In contrast to simple PAHs, that do not interact strongly with solid H2O, the nitrogen atoms in PANHs are potentially capable of hydrogen bonding with H2O. Whereas the IR spectrum of phenanthridine in H2O is similar to that of the same compound isolated in an argon matrix, quinoline absorptions shift up to 16 cm(sup -1) (0.072 mm) between argon and H2O. Thus, astronomers will not always be able to rely on IR band positions of matrix isolated PANHs to correctly interpret the absorptions of PANHs frozen in H2O ice grains. Furthermore, our data suggest that relative band areas also vary, so determining column densities to better than a factor of 3 will require knowledge of the matrix in which the PANH is embedded and laboratory studies of relevant samples.

Bernstein, M. P.↗

PAH Products and Processing by Different Energy Sources

Isoviolanthrene (C34H18), a polycyclic aromatic hydrocarbon (PAH) molecule, was studied via matrix isolation in argon and water at 20 K. Infrared spectroscopy was performed in situ where samples were irradiated using ultraviolet light. Experimental spectra were compared to theoretical spectra for vibrational band assignment, determination of the corresponding A-values, and photoproduct identification. Isoviolanthrene was also deposited as a thin film and irradiated with different energy sources: ultraviolet photons (10.2 eV), soft electrons (1.5 keV), protons (1.5 MeV), and He+ particles (1.5 MeV), to understand the effects of different energy sources on a PAH. Anions and cations of soviolanthrene were produced as a result of UV photolysis in an argon matrix. Hydrogenand oxygen-rich aromatic photoproducts were produced by ultraviolet photons when isoviolanthrene was isolated in a water matrix. The irradiated PAH thin films results were dependent on the energy source. Irradiation with ultraviolet photons yielded a broad underlying feature centered at 9.6 μm, while bombardment with soft electrons gave a broad feature centered at 7.7 μm. In the case of proton bombardment, no broad feature was detected, in contrast with He+ bombardment that destroyed most of the isoviolanthrene and produced broad features in the C-Hoop and C–H stretching regions. A comparison of astronomical IR emission observations with our experimental results in the mid-infrared range has revealed a similarity between the observed plateaus and the broad features produced by our experiments.

astrochemistry – infrared: ISM – methods: laborato↗

Spectroscopy of Cosmic Carbon Analogs in Inert-Gas Matrices and in the Gas-Phase: Comparative Results and Perspectives for Astrophysics

Recent studies of the spectroscopy of large (up to approx. 50 carbon atoms) neutral and Ionized polycyclic aromatic hydrocarbons (PAHs) and Fullerenes isolated in inert gas matrices will be presented. The advantages and the limitations of matrix isolation spectroscopy for the study of the molecular spectroscopy of interstellar dust analogs will be discussed. The laboratory data will be compared to the astronomical spectra (the interstellar extinction, the diffuse interstellar bands). Finally, the spectra of PAH ions isolated in neon/argon matrices will be compared to the spectra obtained for PAH ion seeded in a supersonic expansion. The astrophysical implications and future perspectives will be discussed.

Salama, Farid↗

Infrared spectra of group III A metal oxides

The measurement of infrared frequencies of metal-oxygen species which could be formed in the matrix and to investigate with an oxygen-18 enrichment study the controversy on the vibrational assignments for the suboxide. Several new molecules, Al3O2, Ga3O, In3O, In4O2, IntaO, IntaO2, and In2WO4, were found by mass spectrometric sampling to exist in extremely minor concentrations in the vapor phase. The latter three species were formed by reaction with the crucible materials and were unimportant for an infrared analysis. The infrared spectroscopic measurements were obtained by the matrix isolation technique of molecular beam sampling. The MO2 species were formed by direct reaction between metal and O2 in the matrix. A C2v structure and an O-M-O bond angle near 40 deg was favored for these molecules by analogy with a similar investigation of the alkali metals. The vibrational frequencies which were determined are given.

Lynch, D. A., Jr.↗

Interstellar problems and matrix solutions

The application of the matrix isolation technique to interstellar problems is described. Following a brief discussion of the interstellar medium (ISM), three areas are reviewed in which matrix experiments are particularly well suited to contribute the information which is sorely needed to further understanding of the ISM. The first involves the measurement of the spectroscopic properties of reactive species. The second is the determination of reaction rates and the elucidation of reaction pathways involving atoms, radicals, and ions which are likely to interact on grain surfaces and in grain mantles. The third entails the determiantion of the spectroscopic, photochemical, and photophysical properties of interstellar and cometary ice analogs. Significant, but limited, progress has been made in these three areas, and a tremendous amount of work is required to fully address the variety of unique chemical and spectroscopic questions posed by the astronomical observations.

Allamandola, Louis J.↗

Alteration and formation of rims on the CM parent body

All types of coarse-grained components in CM chondrites are surrounded by fine-grained dust coatings, but the origin of these rims is not yet clear. Although a strictly nebular origin seems likely for rims in the relatively unaltered type 3 chondrites, the rims in CM chondrites are dominated by secondary alteration phases. It has been argued that either the coarse-grained cores accreted altered rim materials while still in the nebula or that alteration of primary rim phases occurred on the CM parent body. To constrain the origin of alteration phases in rim material, we have analyzed the textures and mineral associations from 10 CM chondritic falls by optical and scanning electron microscopy. Our results indicate that the secondary phases in CM chondritic rims were produced by parent body fluid-rock interactions which redefined some primary rim textures and may have produced, in some cases, both coarse-grained components and the rims that surround them. Textural features demonstrate the interactive exchange of alteration fluids between rims, matrix, and chondrules on the CM parent body. For example, most matrix-rim contacts are gradational, suggesting the synchronous alteration of both components. Several observations suggest the possibility of in situ rim production. For example, tochilinite and phyllosilicates commonly form rims around matrix carbonates, which are generally believed to have precipitated from alteration fluids on the CM parent body. This suggests that the rims surrounding matrix carbonates may also have been produced by alteration processes. Partially replaced chondrule olivines bear a striking resemblance to many rimmed olivines in the matrix which suggests, by analogy, that site-specific precipitation of S-bearing phases may also be responsible for the occurrence of many tochilinite-rich rims around isolated matrix olivines. Non-silicate rims precipitate around olivines of any composition, but the process is most effective for fayalitic olivines. Most of the remaining olivines in CM chondrites are relatively Mg-rich, which suggests that the precipitation of S-bearing rims on olivines may not have been an important process in the aqueous alteration of CM chondrites. We conclude that: (1) precursor rim materials in CM chondrites were subjected to pervasive aqueous alteration on the CM parent body; and (2) textures and mineral associations observed in CM chondrites also suggest the possibility of in situ rim production.

Browning, Lauren B.↗

Matrix spectroscopic studies of chlorine atom-ozone reaction products

A spectroscopic study is presented of the matrix-isolated products of the direct combination reaction of chlorine atoms with ozone and of the microwave discharge reaction of chlorine and oxygen. Infrared spectra in the wavenumber range 2000 to 200 per cm were recorded for reaction products trapped by the condensation of a matrix of solid argon. Evidence for the formation of the ClO radical as well as the ClOO and ClClO radicals during the direct chlorine-ozone reaction is obtained, however no evidence is found for the presence of asymmetric ClO3 under conditions thought favorable for its formation. The ClO molecule is also observed following the microwave discharge reaction of chlorine and oxygen in argon in the isotopic forms (Cl-35)(O-16), (Cl-37)(O-16), (Cl-35)(O-18), and (Cl-37)(O-18). It is noted that the vibrational frequency for the (Cl-35)(O-16) radical at 849.2 per cm is blue-shifted 5 per cm above its gas-phase fundamental.

Carter, R. O., III↗

In Crystallo Photochemistry: Reimagining Synthetic Tractability with Transparent Single-Crystalline Flasks

Expanding the boundaries of synthetic tractability of what molecules can be synthesized and isolated is an eternal challenge for synthetic chemists. The development of new synthetic methods and strategies enables the properties and potential functions of novel molecular targets to be experimentally evaluated. In the context of catalysis, predictable synthetic strategies are often available to access kinetically persistent intermediates such as catalyst resting states. In contrast, synthesis and characterization of the reactive intermediates are often not possible due to the fleeting lifetimes of these species. In crystallo photochemistry combines single-crystal matrix isolation with cryogenic photochemistry to enable reactive intermediates to be synthesized under conditions in which they are persistent and can be (crystallographically) characterized. This Outlook highlights key achievements of in crystallo photochemistry as well as discusses opportunities and challenges that confront realization of the potential of in crystallo synthesis to redefine the boundaries of synthetic tractability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Mid-Infrared Absorption Spectra of Neutral PAHs in Dense Interstellar Clouds

Polycyclic aromatic hydrocarbons (PAHs) are common throughout the universe and are expected to be present in dense interstellar clouds. In these environments, some P.4Hs may be present in the gas phase, but most should be frozen into ice mantles or adsorbed onto dust grains and their spectral features are expected to be seen in absorption. Here we extend our previous work on the infrared spectral properties of the small PAH naphthalene (C10H8) in several media to include the full mid-infrared laboratory spectra of 11 other PAHs and related aromatic species frozen in H2O ices. These include the molecules 1,2-dihydronaphthalene, anthracene, 9,1O-dihydroanthracene, phenanthrene, pyrene, benzo[e]pyrene, perylene, benzo(k)fluoranthene, pentacene, benzo[ghi]perylene, and coronene. These results demonstrate that PAHs and related molecules, as a class, show the same spectral behaviors as naphthalene when incorporated into H2O-rich matrices. When compared to the spectra of these same molecules isolated in inert matrices (e.g., Ar or N2), the absorption bands produced when they are frozen in H2O matrices are broader (factors of 3-10), show small position shifts in either direction (usually < 4/cm, always < 10/cm), and show variable changes in relative band strengths (typically factors of 1-3). There is no evidence of systematic increases or decreases in the absolute strengths of the bands of these molecules when they are incorporated in H2O matrices. In H2O-rich ices, their absorption bands are relatively insensitive to concentration over the range of 10 < H2O/PAH < 200): The absorption bands of these molecules are also insensitive to temperature over the 10 K < T < 125 K range, although the spectra can show dramatic changes as the ices are warmed through the temperature range in which amorphous H2O ice converts to its cubic and hexagonal crystalline forms (T > 125 Kj. Given the small observed band shifts cause by H2O, the current database of spectra from Ar matrix-isolated neutral PAHs and related molecules should be useful for the search for these species in dense clouds on the basis of observed absorption band positions. Furthermore, these data permit determination of column densities to better than a factor of 3 for PAHs in dense clouds. Column density determination of detected aromatics to better than a factor of 3 will, however, require good knowledge about the nature of the matrix in which the PAH is embedded and laboratory studies of relevant samples.

Bernstein, M. P.↗

ESO Diffuse Interstellar Bands Large Exploration Survey (EDIBLES) - Merging Observations and Laboratory Data

The Diffuse Interstellar Bands (DIBs) are a set of ~500 absorption bands that are detected in the spectra of stars with interstellar clouds in the line of sight. DIBs are found from the NUV to the NIR in the spectra of reddened stars spanning different interstellar environments in our local, and in other galaxies. DIB carriers are a significant part of the interstellar chemical inventory. They are stable and ubiquitous in a broad variety of environments and play a unique role in interstellar physics/chemistry. It has long been realized that the solving of the DIB problem requires a strong synergy between astronomical observations, laboratory astrophysics, and astrophysical modeling of line-of-sights. PAHs are among the molecular species that have been proposed as DIB carriers. We will present an assessment of the PAH-DIB model in view of the progress and the advances that have been achieved over the past years through a series of studies involving astronomical observations of DIBs, laboratory simulation of interstellar analogs for neutrals and ionized PAHs, theoretical calculations of PAH spectra and the modelization of diffuse and translucent interstellar clouds. We will present a summary of what has been learned from these complementary studies, the constraints that can now be derived for the PAHs as DIB carriers in the context of the PAH-DIB model and how these constraints can be applied to the EDIBLES project. The spectra of several neutral and ionized PAHs isolated in the gas phase at low temperature have been measured in the laboratory under experimental conditions that mimic interstellar conditions and are compared with an extensive set of astronomical spectra of reddened, early type stars. The comparisons of astronomical and laboratory data provide upper limits for the abundances of specific neutral PAH molecules and ions along specific lines-of-sight. Something that is not attainable from infrared observations alone. We present the characteristics of the laboratory facilities, MIS and COSmIC, that have been developed for this study and discuss the findings resulting from the comparison of the laboratory data with high resolution, high S/N ratio astronomical observations. MIS stands for Matrix Isolation Spectroscopy, a well-proven technique for isolating cold molecular species in inert solid environments. COSmIC stands for Cosmic Simulation Chamber. It combines a supersonic free jet expansion with discharge plasma and high-sensitivity cavity ringdown spectroscopy and time-of-flight mass spectrometry detection tools for the generation and the detection of cold, isolated gas-phase molecules and ions under experimental conditions that closely mimic interstellar conditions. The column densities of the individual neutral PAH molecules and ions probed in these surveys are derived from the comparison of these unique laboratory data with high resolution, high S/N ratio astronomical observations. The comparisons of astronomical and laboratory data lead to clear and unambiguous conclusions regarding the expected abundances for PAHs of various sizes and charge states in the interstellar environments probed in the surveys. Band profile comparisons between laboratory and astronomical spectra lead to information regarding the molecular structures and characteristics associated with the DIB carriers in the corresponding lines-of-sight. These quantitative surveys of neutral and ionized PAHs in the optical range open the way for unambiguous quantitative searches of PAHs and complex organics in a variety of interstellar and circumstellar environments.

astrophysics↗

Infrared spectoscopy of Triton and Pluto ice analogs: The case for saturated hydrocarbons

The infrared transmission spectra and photochemical behavior of various organic compounds isolated in solid N2 ices, appropriate for applications to Triton ad Pluto, are presented. It is shown that excess absorption in the surface spectra of Triton and Pluto, i.e., absorption not explained by present models incorporating molecules already identified on these bodies (N2, CH4, CO, and CO2), that starts near 4450/cm (2.25 microns) and extends to lower frequencies, may be due to alkanes (C(n)H(2n+2)) and related molecules frozen in the nitrogen. Branched and linear alkanes may be responsible. Experiments in which the photochemstry of N2: CH4 and N2: CH4: CO ices was explored demonsrtrate that the surface ices of Triton and Pluto may contain a wide variety of additional species containing H, C, O, and N. Of these, the reactive molecule diazomethane, CH2N2, is particularly important since it may be largely responsible for the synthesis of larger alkanes from CH4 and other small alkanes. Diazomethane would also be expected to drive chemical reactions involving organics in the surface ices of Triton and Pluto toward saturation, i.e., to reduce multiple CC bonds. The positions and intrinsic strengths (A values) of many of the infrared absorption bands of N2 matrix-isolated molecules of relevance to Triton and Pluto have also been determined. These can be used to aid in their search and to place constraints on their abundances.

Bohn, Robert B.↗

Pyrolysis Reactions of (2-Chloroethyl)benzene

Pyrolysis of polyvinyl chloride (PVC) is considered an alternative to traditional, mechanical methods of recycling. However, there is insufficient research conducted on the thermal decomposition pathways of PVC, particularly the fate of chlorinated hydrocarbons generated during the chemical recycling process. One significant product from the pyrolysis of PVC is (2- chloroethyl)benzene. Using a hyperthermal tubular reactor and matrix-isolation FTIR techniques, the pyrolysis products of gasphase (2-chloroethyl)benzene were identified. Following pyrolysis at 1400 K, the FTIR spectra indicated the formation of HCl, styrene, phenylacetylene, benzene, vinylacetylene, acetylene, propyne, ethylene, and propargyl radical.

Aromatic compounds↗