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At least 649 records · Page 36

Theoretical infrared spectra of some model polycyclic aromatic hydrocarbons - Effect of ionization

In order to test the hypothesis of ionized PAHs as possible carriers of the UIR bands, we realized a computational exploration on selected PAHs of small dimension in order to identify which changes ionization would induce on their IR spectra. In this study we performed ab initio calculations of the spectra of neutral and positively ionized naphthalene, anthracene, and pyrene. The results are significantly important. The frequencies in the cations are slightly shifted with respect to the neutral species, but no general conclusion can be reached from the three molecules considered. By contrast, the relative intensities of most vibrations are strongly affected by ionization, leading to a much better agreement between the calculated CH/CC vibration intensity ratios and those deduced from observations.

De Frees, D. J.↗

3.3 and 11.3 micron images of HD 44179 - Evidence for an optically thick polycyclic aromatic hydrocarbon disk

Images of HD 44179 (the Red Rectangle) obtained in the 3.3 and 11.3 micron emission bands show two different spatial distributions. The 3.3 micron band image is centrally peaked and slightly extended N-S while the 11.3 micron image shows a N-S bipolar shape with no central peak. If the 3.3 micron band image shows the intrinsic emission of the 11.3 micron band, then the data suggest absorption of the 11.3 micron emission near the center of HD 44179 by a disk with an optical depth of about one, making HD 44179 the first object in which the IR emission bands have been observed to be optically thick. Since there is no evidence of absorption of the 3.3 micron emission band by the disk, the absorption cross section of the 3.3 micron band must be substantially less than for the 11.3 micron band. Since the 3.3 and 11.3 micron bands are thought to arise from different size PAHs, the similar N-S extents of the two images implies that the ratio of small to large PAHs does not change substantially with distance from the center.

Bregman, Jesse D.↗

Laboratory evidence for ionized polycyclic aromatic hydrocarbons in the interstellar medium

The infrared absorption from neutrals and cations of four PAHs - naphthalene, anthracene, pyrene, and perylene - integrated over the spectral regions corresponding to the interstellar bands are compared with astronomical observations. It is found that the interstellar bands cannot be explained solely on the basis of neutral PAH species, but that cations must be a significant, and in some cases dominant, component.

Szczepanski, Jan↗

Polycyclic aromatic hydrocarbons in the atmospheres of Titan and Jupiter

PAHs are important components of the interstellar medium and carbonaceous chondrites, but have never been identified in the reducing atmospheres of the outer solar system. Incompletely characterized complex organic solids (tholins) produced by irradiating simulated Titan atmospheres reproduce well the observed UV/visible/IR optical constants of the Titan stratospheric haze. Titan tholin and a tholin generated in a crude simulation of the atmosphere of Jupiter are examined by two-step laser desorption/multiphoton ionization mass spectrometry. A range of two- to four-ring PAHs, some with one to four alkylation sites, are identified, with a net abundance of about 0.0001 g/g (grams per gram) of tholins produced. Synchronous fluorescence techniques confirm this detection. Titan tholins have proportionately more one- and two-ring PAHs than do Jupiter tholins, which in turn have more four-ring and larger PAHs. The four-ringed PAH chrysene, prominent in some discussions of interstellar grains, is found in Jupiter tholins.

Sagan, Carl↗

The synthesis and purification of aromatic hydrocarbons IV : 1,2,3-trimethylbenzene

A six gallon quantity of 1,2,3-trimethylbenezene was prepared and purified in a four-step synthesis involving the condensation of 1,3-pentadiene with crotonaldehyde. The dimethylcyclohexencarboxaldehydes formed were hydrogenated to give the corresponding isomeric dimethylcyclohexylcarbinols. The dehydration of the carbinols and the subsequent dehydrogenation of the trimethylcyclohexenes yielded the 1,2,3-trimethylbenzene. The overall yield was 24 percent; the physical properties of the materials are given.

Lamberti, J M↗

The synthesis and purification of aromatic hydrocarbons V : 1-ethyl-3-methylbenzene

The method used for the synthesis and purification of an 8-gallon quantity of 1-ethyl-3-methylbenzene from m-creosol consists in obtaining m-methylcyclohexanone from m-creosol by hydrogenation followed by oxidation, condensation of the ketone with ethylmagnesium bromide, dehydration of the tertiary alcohol obtained, and the dehydration of the olefins to 1-ethyl-3-methylbenzene. A yield of 28 percent of the theoretical was obtained from 98 percent commercial m-creosol. The physical properties of the 1-ethyl-3-methylbenzene are compared with selected values from the literature.

Ebersole, Earl R↗

New aromatic activated dihalides and bisphenol monomers for the preparation of novel poly(arylene ethers)

The goal of this research program was to synthesize a series of unique monomers of type I to be utilized at NASA-Langley in the preparation of new poly(arylene ether ketones), poly(arylene ether ketosulfones), and poly(arylene ether ketophosphine oxides). These A-A and A-B monomer systems, which possess activated aryl halide and/or phenolic end groups, are accessible via condensation reactions of appropriately substituted aryl acetonitrile carbanions with activated aryl dihalides followed by oxidative decyanation.

Wolfe, James F.↗

The photoelectric heating mechanism for very small graphitic grains and polycyclic aromatic hydrocarbons

We have theoretically modeled the gas heating associated with the photoelectric ejection of electrons from a size distribution of interstellar carbon grains which extends into the molecular domain. We have considered a wide range of physical conditions for the interstellar gas (1 less than G(sub 0) less than 10(exp 5), with G(sub 0) being the intensity of the incident far-UV field in units of the Habing interstellar radiation field; 2.5 x 10( exp -3) less than n(sub e) less than 75/cu cm, with n(sub e) being the electron density; 10 less than T less than 10,000 K, with T being the gas temperature). The results show that about half of the heating is due to grains less than 1500 C atoms (less than 15 A). The other half originates in somewhat larger grains (1500-4.5 x 10(exp 5) C atoms; 15 less than 100 A). While grains larger than this do absorb about half of the available far-UV photons, they do not contribute appreciably to the gas heating. This strong dependence of gas heating on size results from the decrease in yield and from the increased grain charge (hence larger Coulomb losses) with increasing grain size. We have determined the net photoelectric heating rate and evaluated a simple analytical expression for the heating efficiency, dependent only on G(sub 0), T, and n(sub e). This expression is accurate to 3% over the whole parameter range and is valid up to gas temperatures of 10(exp 4) K, at which point the dominant gas-dust heat exchange mechanism becomes the recombination of electrons with grains rather than photoelectric ejection. The calculated heating efficiency for neutral grains is in good agreement with that derived from observations of the diffuse interstellar clouds. Our results also agree well with the Far Infrared Absolute Spectrometer (FIRAS) observations on the Cosmic Background Explorer Satellite. Finally, our photoelectric heating efficiency is compared to previous studies.

Bakes, E. L. O.↗

Investigation of Oxygen-Induced Quenching of Phosphorescence in Photoexcited Aromatic Molecules by Positron Annihilation Spectroscopy

Platinum OctaEthyl Porphyrin (Pt.OEP) is an efficient phosphor under ultraviolet excitation. The phosphorescent triplet state P(T(Sup 1)) is readily quenched by the oxygen O2 molecules. This phenomenon is being utilized as the basis for global air pressure measurements in aerodynamic facilities at various laboratories. The exact mechanism by which O2 molecules quench the P(T(Sup 1) approaches P(S(Sub O)) transitions is still unknown. The diamagnetic singlet states P(S(Sub n)), which feed P(T(Sub 1)) states via intersystem crossings, would presumably not be affected by O2. It must be only the magnetic P(T(Sub 1)) states, which can interact with the paramagnetic O2 molecules, that are affected. However, our positron lifetime and Doppler broadening studies suggest the formation of O2P(S(Sub n)), complexes which can also eventually reduce the population of the P(T(Sub 1)) states (i.e., quench phosphorescence). This reduction is possible because higher triplet states in (Pt.OEP) are admixed with the P(S(Sub 1)), states via spin orbit interactions. The experimental procedures and the results of various measurements are presented in this paper.

Singh, Jag J.↗

The Infrared Emission Features and Polycyclic Aromatic Hydrocarbons

The infrared evidence which supports the PAH hypothesis is briefly summarized. Rather than presenting a general discussion of these assignments, this paper focuses on the spectroscopic issues raised by recent observational and experimental developments. These issues include: the position and profile of the '1310/cm ('7.7' microns) feature, the position and intensities of the bands in the 910-710 1/cm (11-1 microns) region, the newly detected 1900 1/cm (5.3 microns) band, and the spatial and spectral variations in the 3000 1/cm (3 microns) region as well as in the 12 and 25 microns InfraRed Astronomy Satellite (IRAS) bands. It is concluded that the infrared evidence for interstellar PAH's and PAH-related species is compelling.

Allamandola, L. J.↗

Molecular Static Third-Order Polarizabilities of Carbon-Cage Fullerenes and their Correlation with Three Geometric Parameters: Group Order, Aromaticity, and Size

Calculations were performed on the valence contribution to the static molecular third-order polarizabilities (gamma) of thirty carbon-cage fullerenes (C60, C70, five isomers of C78, and twenty-three isomers of C84). The molecular structures were obtained from B3LYP/STO-3G calculations. The values of the tensor elements and an associated numerical uncertainty were obtained using the finite-field approach and polynomial expansions of orders four to eighteen of polarization versus static electric field data. The latter information was obtained from semiempirical calculations using the AM1 hamiltonian.

Moore, Craig E.↗

The Production of Polycyclic Aromatic Hydrocarbon Anions in Inert Gas Matrices Doped with Alkali Metals. Electronic Absorption Spectra of the Pentacene Anion (C22H14(-))

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).

Halasinski, Thomas M.↗