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At least 217 records · Page 12

Photo-thermo-dissociation. I - A general mechanism for destroying molecules

Photothermodissociation (PTD) of an isolated molecule is the name of the process when a photon is absorbed by an electronic transition, the energy is transferred to the vibrations (hot molecule) and then an atom or a fragment is ejected. A statistical physics treatment is presented that goes beyond the thermal approximation and fully takes into account the isolation of the system. A model is given that permits an explicit calculation of the ejection rates of hydrogen and carbon fragments from aromatic molecules as a function of their size and internal energy. Then, the lifetime of species against PTD in different astronomical radiation fields will result when a precise dynamical evolution of their internal energy can be established.

Leger, A.↗

Positronium ions and molecules

Recent theoretical studies on positronium ions and molecules are discussed. A positronium ion is a three particle system consisting of two electrons in singlet spin state, and a positron. Recent studies include calculations of its binding energy, positron annihilation rate, and investigations of its doubly excited resonant states. A positronium molecule is a four body system consisting of two positrons and two electrons in an overall singlet spin state. The recent calculations of its binding energy against the dissociation into two positronium atoms, and studies of auto-detaching states in positronium molecules are discussed. These auto-dissociating states, which are believed to be part of the Rydberg series as a result of a positron attaching to a negatively charged positronium ion, Ps-, would appear as resonances in Ps-Ps scattering.

Ho, Y. K.↗

Positron-molecule bound states and positive ion production

The interaction was studied of low energy positrons with large molecules such as alkanes. These data provide evidencce for the existence of long lived resonances and bound states of positrons with neutral molecules. The formation process and the nature of these resonances are discussed. The positive ions produced when a positron annihilates with an electron in one of these resonances were observed and this positive ion formation process is discussed. A review is presented of the current state of the understanding of these positron-molecule resonances and the resulting positive ion formation. A number of outstanding issues in this area is also discussed.

Leventhal, M.↗

New observations of interstellar organic molecules

Discussed here are new observations of 3-carbon-containing interstellar molecules which play an important role in the chemistry of dense molecular clouds: protonated carbon dioxide, formic acid, and propynal. In 1984 a new oxide of carbon, C3O, was discovered in the interstellar medium (Matthews et al. 1984; Brown et al. 1985). Theoretical models suggest that C3O is produced by dissociative electron recombination with the ion H3C3O+. Although no laboratory data for the branching ratios of such a recombination exist, it seemed to us likely that additional products would include H2C3O. This molecule has more than one isomeric form, but one stable species is propynal (HC2CHO), which had been suggested as a possible interstellar molecule by Winnewisser (1973). In observations at the National Radio Astronomy Observatory 43 m telescope in Green Bank earlier this year, researchers detected a line in the cold cloud TMC-1 which they assign to the 2(0,2)-1(0,1) transition of propynal. The observed line agrees with the laboratory frequency to well within the experimental uncertainty a few parts in 10 to the 7th power. Researchers sought and failed to detect the corresponding 2(1,1)-1(1,0) line, which is understandable given the presence of both a and b components of the electric dipole moment in propynal. The b type transitions will drain population from energy levels with K(sub p) does not equal 0 into the K(sub p) equal 0 stack. If the researchers' assignment is correct, this is the first interstellar detection of propynal. Assuming typical rotational temperatures for TMC-1 and that the line is optically thin, the column density determined is about 5 times 10 to the 12th power cm to the -2nd power, or about three times that for C3O. Formic acid (HCOOH) was the first organic acid to be observed in the interstellar medium, in the Galactic center source Sgr B2. The only other interstellar detection has been recently made in the giant molecular cloud in Orion. As part of the same project that led to the detection of propynal, researchers sought formic acid in the nearby, cold dark clouds TMC-1 and L134N. It is seen only in L134N. This difference between the two clouds appears to be consistent with a model in which the oxygen/carbon ratio is higher in L134N. This would be consistent with the higher abundances for SO and SO2, observed in that cloud, and the higher abundances of many carbon-rich species in TMC-1 (Irvine et al. 1985).

Irvine, W. M.↗

The binding energies of one and two water molecules to the first transition-row metal positive ions. II

The present investigation of H2O's binding energy to transition-metal ions proceeds from the D(2h) structure and bends the two water molecules out of plane. The molecule is constrained to have C(2v) symmetry, so that each water molecule and metal ion lies on a plane. The ground states are bent only for Mn(H2O)2(+) and Zn(H2O)2(+), where only 4s4p hybridization is energetically favorable; 4s4p hybridization reduces repulsion.

Rosi, Marzio↗

3.3 micron emission from ultraviolet excitation of some aromatic molecules

Infrared emissions are observed from photoexcitation of benzene, naphthalene, phenanthrene, anthracene, pyrene, and their methyl derivatives in the gas phase at 193 nm using an ArF laser as a light source. An emission band with peak at 3.3 microns is observed from all the molecules studied. This band is attributed to the aromatic C-H stretching vibrational modes. In addition to the 3.3-microns band, an emission band at 3.4-3.6 microns is observed from photoexcitation of the methyl derivatives, which is attributed to the C-H stretching vibrational modes of the CH3 group. The observed spectra are compared with the IR emission bands observed in many astronomical objects. The current laboratory data lend support to a model in which PAH molecules are responsible for the 'unidentified' interstellar IR emissions. IR emissions from the 193-nm excitation of several interstellar molecules other than PAHs are also observed, but they are quite different from the interstellar IR bands.

Shan, Jun↗

Photoabsorption and photodissociation of molecules important in the interstellar medium

The photo absorption, photo dissociation, and fluorescence cross sections of interstellar molecules and radicals were measured in the vacuum ultraviolet region. These quantitative optical data are useful for understanding of the formation and destruction processes of molecules under the intense interstellar W radiation field. Infrared (IR) emissions from W excitation of aromatic molecules were also observed in this research program. The research results are useful for studying the sources of the 'unidentified' interstellar infrared (UIR) emission bands.

Lee, Long C.↗

Internal vibrations of a molecule consisting of rigid segments. I - Non-interacting internal vibrations

For molecular crystals, a procedure is proposed for interpreting experimentally determined atomic mean square anisotropic displacement parameters (ADPs) in terms of the overall molecular vibration together with internal vibrations with the assumption that the molecule consists of a set of linked rigid segments. The internal librations (molecular torsional or bending modes) are described using the variable internal coordinates of the segmented body. With this procedure, the experimental ADPs obtained from crystal structure determinations involving six small molecules (sym-trinitrobenzene, adenosine, tetra-cyanoquinodimethane, benzamide, alpha-cyanoacetic acid hydrazide and N-acetyl-L-tryptophan methylamide) have been analyzed. As a consequence, vibrational corrections to the bond lengths and angles of the molecule are calculated as well as the frequencies and force constants for each internal torsional or bending vibration.

He, X. M.↗

Fourier transform spectroscopy of the Swan (d(sup 3)pi(sub g) - a(sup 3)pi(sub u)) system of the jet-cooled C2 molecule

The Swan (d(sup 3)pi(sub g) - a(sup 3)pi(sub u)) system of the C2 molecule was produced in a jet-cooled corona excited supersonic expansion of helium using diazoacetonitrile as a percursor molecule. This spectrum was recorded using the McMath Fourier transform spectrometer of the National Solar Observatory at Kitt Peak. A total of nine bands with v prime = 0 to 3 and v prime prime = 0 to 4 in the range 16,570-22,760/cm were observed and rotationally analyzed. The C2 molecules in this source had a rotational temperature of only 90 K so that only the low-J lines were present in the spectrum. In some sense the low temperatures in the jet source simulate conditions in the interstellar medium. The Swan system of C2 was also produced in a composite wall hollow cathode made Al4C3/Cu, and the rotational structure of the 1-0, 2-1, 3-2, 0-0, and 1-1 bands were analyzed. The data obtained from both these spectra were fitted together along with some recently published line positions. The rotational constants, lambda doubling parameters and the vibrational constants were estimated from this global fit. Our work on jet-cooled C2 follows similar work on the violet and red systems of CN. A summary of this CN work is also presented. also presented.

Prasad, C. V. V.↗

Detection of interstellar N2O: A new molecule containing an N-O bond

A new interstellar molecule, N2O, known as nitrous oxide or 'laughing gas,' has been detected using the NRAO 12 m telescope. The J = 3 - 2, 4 - 3, 5 - 4, and 6 - 5 rotational transitions of this species at 75, 100, 125, and 150 GHz, respectively, were observed toward Sgr B2(M). The column density derived for N2O in this source is N(sub tot) approx. 10(exp 15)/sq. cm, which corresponds to a fractional abundance of approx. 10(exp -9), relative to H2. This value implies abundance ratios of N2O/NO approx. 0.1 and N2O/HNO approx. 3 in the Galactic center. Such ratios are in excellent agreement with predictions of ion-molecule models of interstellar chemistry using early-time calculations and primarily neutral-neutral reactions. N2O is the third interstellar molecule detected thus far containing an N-O bond. Such bonds cannot be so rare as previously thought.

Ziurys, L. M.↗

Using naturally occurring polysaccharides to align molecules with nonlinear optical activity

The Biophysics and Advanced Materials Branch of the Microgravity Science and Applications Division at Marshall Space Flight Center has been investigating polymers with the potential for nonlinear optical (NLO) applications for a number of years. Some of the potential applications for NLO materials include optical communications, computing, and switching. To this point the branch's research has involved polydiacetylenes, phthalocyanins, and other synthetic polymers which have inherent NLO properties. The aim of the present research is to investigate the possibility of using naturally occurring polymers such as polysaccharides or proteins to trap and align small organic molecules with useful NLO properties. Ordering molecules with NLO properties enhances 3rd order nonlinear effects and is required for 2nd order nonlinear effects. Potential advantages of such a system are the flexibility to use different small molecules with varying chemical and optical properties, the stability and cost of the polymers, and the ability to form thin, optically transparent films. Since the quality of any polymer films depends on optimizing ordering and minimizing defects, this work is particularly well suited for microgravity experiments. Polysaccharide and protein polymers form microscopic crystallites which must align to form ordered arrays. The ordered association of crystallites is disrupted by gravity effects and NASA research on protein crystal growth has demonstrated that low gravity conditions can improve crystal quality.

Prasthofer, Thomas↗

Mechanism of phosphorescence quenching in photomagnetic molecules determined by positron annihilation spectroscopy

Platinum Octaethyl Porphyrin (Pt.OEP) is an efficient phosphor under ultraviolet excitation. The phosphorescent triplet state (T(sub 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 (T(sub 1)-S(sub 0)) transitions is still unknown. The diamagnetic S(sub n) singlet states, which feed T(sub 1) states via intersystem crossings, would presumably not be affected by O2. It must be the magnetic 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 (S(sub n).02) complexes which can also eventually reduce the population of the T(sub 1) states (i.e. quench phosphorescence). This is possible since higher triplet states in (Pt-OEP) are admixed with the S(sub n) states via spin orbit interactions. The experimental procedures and the results of various measurements are discussed in this paper.

Singh, Jag J.↗

Mechanism of phosphorescence quenching in photomagnetic molecules determined by positron annihilation spectroscopy

Platinum Octaethyl Porphyrin (Pt.OEP) is an efficient phosphor under ultraviolet excitation. The phosphorescent triplet state (T(sub 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 (T(sub 1) - S(sub 0)) transitions is still unknown. The diamagnetic S(sub n) singlet states, which feed T(sub 1) states via intersystem crossings, would presumably not be affected by O2. It must be the magnetic 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 (S(sub n) central dot O2) complexes which can also eventually reduce the population of the T(sub 1) states (i.e. quench phosphorescence). This is possible since higher triplet states in (Pt.OEP) are admixed with the S(sub n) states via spin orbit interactions. The experimental procedures and the results of various measurements are discussed in this paper.

Singh, Jag J.↗

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.↗

Analyses at High Spatial Resolution of Organic Molecules in Extraterrestrial Samples: Two-Step Laser Mass Spectrometry: Search for Polycyclic Aromatic Hydrocarbons in Antarctic Meteorite and Micrometeorite Samples

Perhaps the best way to summarize the past three-year grant period is to cite the publications and present a brief synopsis of each: 1. "Indigenous Polycyclic Aromatic Hydrocarbon Molecules in Circumstellar Graphite Grains." Bulk C-12/C-13 isotope ratios observed in some graphite grains extracted from primitive meteorites point strongly to a circumstellar origin. By applying our technique of microprobe two-step laser desorption laser ionization mass spectrometry ((mu)L(sup 2)MS) to individual circumstellar graphite grains we have measured the C-12/C-13 isotope ratio of various polycyclic aromatic hydrocarbons (PAHS) found in these grains. 2. "Deuterium Enrichments in Cluster IDPS," Large enrichments in the D/H isotope ratios in IDPs likely arise from the preservation of presolar molecules. 3. "Evidence for thermalization of surface-disorder molecules at heating rates of 10(exp 8) K/s". A careful study of the ((mu)L(sup 2)MS) of aniline-d(sub 7) from a single-crystal surface (0001) of sapphire (al2O3) shows that all measured properties are consistent with a thermal mechanism for desorption. 4. "Search for past life on Mars; possible relic biogenic activity in Martian meteorite ALH 84001. The authors examined the Martian meteorite ALH 84001 and found several lines of evidence compatible with existence of past primitive (single-cell) life on early Mars. 5. "Microprobe two-step laser mass spectrometry as an analytical tool for meteorite samples". THis paper presents a comprehensive review of (mu)L(sup 2)MS and how this technique can be applied to meteoritic samples. 6. "Indigenous polycyclic aromatic hydrocarbons in circumstellar graphite grains from primitive meteorites". The C-12/C-13 isotope ratios were measured for PAHs in a total of 89 spherical graphite grains. 7. "Observation of indigenous polycyclic aromatic hydrocarbons in "Giant" carbonaceous antarctic micrometeorites." The (mu)L(sup 2)MS method was used to establish the nature and distribution of PAHs in fragments of fifteen (approx. 200 microns) carbonaceous antarctic micrometeorites (AMMs). 8. "Evidence for the extraterrestrial origin of polycyclic aromatic hydrocarbons in the Martian meteorite ALH 84001" We have undertaken additional contamination studies of ALH 84001.

Zare, Richard N.↗

Behavior of Molecules on Interstellar Grains: Application of the Langevin Equation and Iterative Extended Huckel

The Langevin equation was used to explore an adsorbate desorption mechanism. Calculations were performed using iterative extended Huckel on a silica model site with various small adsorbates, e.g., H, CH, OH, NO, CO. It was found that barriers to free traversal from one site to another are substantial (approximately 3 - 10 eV). A bootstrap desorption mechanism for some molecules in the process of forming at a site also became apparent from the calculations. The desorption mechanisms appear to be somewhat balanced by a counterforce--the attraction of sites for the newly desorbed molecule. The order of attraction to a silica grain site for the diatomic molecules considered was OH > CH > CO > NO, when these entities were sufficiently distant. The nature of the silica grain and that of the "cold" desorption mechanism, when considered together, suggest that the abundance of very small grains might be less common than anticipated.

Aronowitz. Sheldon↗

Application of Coupled-Cluster Methods to the Prediction and Interpretation of the Spectra of Molecules of Interest in Atmospheric Chemistry

The quality of fundamental vibrational frequencies determined using the CCSD(T) method (singles and doubles coupled-cluster theory plus a perturbational estimate of the effects of connected triple excitations) is shown to be very good, usually predicting band centers to within +/-8/cm. This approach is applied to several molecules of interest in atmospheric chemistry, including HNO, NO2(+), H2CO, and HOCl. The HNO molecule displays a large and unusual anharmonicity in the H-N stretch. For the calculation of ultraviolet (UV) spectra, the linear response CCSD (LRCCSD) approach (which is equivalent to EOM-CCSD) has been shown to yield vertical excitation energies that are accurate to approximately 0.1 eV for singly excited electronic states. This method together with more approximate methods is used to examine the UV spectra of several molecules important in stratospheric chemistry, including HOCl, Cl2O, ClOOCl, ClOOH, and HOOH.

Lee, Timothy J.↗

A FFT Method for the Quasiclassical Selection of Initial Ro-Vibrational States of Triatomic Molecules

This paper describes the use of an exact fast Fourier transform (FFT) method to prepare specified vibrational-rotational states of triatomic molecules. The method determines the Fourier coefficients needed to describe the coordinates and momenta of a vibrating-rotating triatomic molecule. Once the Fourier coefficients of a particular state are determined, it is possible to easily generate as many random sets of initial cartesian coordinates and momenta as desired. All the members of each set will correspond to the particular vibrational-rotational state selected. For example, in the case of the ground vibrational state of a non-rotating water molecule, the calculated actions of 100 sets of initial conditions produced actions within 0.001 h(bar) of the specified quantization values and energies within 5 cm(sup -1) of the semiclassical eigenvalue. The numerical procedure is straightforward for states in which all the fundamental frequencies are independent. However for states for which the fundamental frequencies become commensurate (resonance states), there are additional complications. In these cases it is necessary to determine a new set of "fundamental" frequencies and to modify the quantization conditions. Once these adjustments are made, good results are obtained for resonance states. The major problems are in labelling the large number of Fourier coefficients and the presence of regions of chaotic motion. Results are presented for the vibrational states of H2O and HCN and the ro-vibrational states of H2O.

Eaker, Charles W.↗