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The interaction of Fe(+) with benzyne is studied using the self-consistent-field (SCF), complete active space SCF, and modified-coupled-pair functional levels of theory. The most stable structure is planar, where the Fe(+) has inserted into the in-plane pi bond, although the C-C bond distance suggests that some in-plane pi bonding remains. This system is compared with Sc(+) bonding to benzyne and other ligands.
During this grant period, the physics of gamma-ray bursts was investigated. A number of new results have emerged. The importance of pair formation in high compactness burst spectra may help explain x-ray flashes; a universal jet shape is a likely explanation for the distribution of jet break times; gravitational waves may be copiously produced both in short bursts from compact mergers and in long bursts arising from collapsars; x-ray iron lines are likely to be due to interaction with the stellar atmosphere of the progenitor; prompt optical flashes from reverse shocks will give diagnostics on the Lorentz factor and the environment; GeV and TeV emission from bursts may be expected in the external shock; etc. The group working with the PI included postdocs Dr. Bing Zhang (now assistant professor at University of Nevada); Dr. Shiho Kobayashi; graduate student Lijun Gou; collaborators Drs. Tim Kallman and Martin Rees. Meszaros shared with Rees and Dr. Bohan Paczynsky the AAS Rossi Prize in 2000 for their work on the theory of gamma ray bursts. The refereed publications and conference proceedings resulting from this research are summarized below. The PI gave a number of invited talks at major conferences, also listed.
Quantum mechanical methods have been used to compute potential energy surfaces for chemical reactions. The reactions studied were among those believed to be important to the NASP and HSR programs and included the recombination of two H atoms with several different third bodies; the reactions in the thermal Zeldovich mechanism; the reactions of H atom with O2, N2, and NO; reactions involved in the thermal De-NO(x) process; and the reaction of CH(squared Pi) with N2 (leading to 'prompt NO'). These potential energy surfaces have been used to compute reaction rate constants and rates of unimolecular decomposition. An additional application was the calculation of transport properties of gases using a semiclassical approximation (and in the case of interactions involving hydrogen inclusion of quantum mechanical effects).
Core integral and electron repulsion integral for 2p-p1 Slater-type orbitals of allyl radical and benzene molecule transformed to Lowdin orthogonalized basis set of atomic orbitals
A previously reported multi-configuration self-consistent field (MCSCF) algorithm based on the generalized Brillouin theorem is extended in order to treat the excited states of polar molecules. In particular, the algorithm takes into account the proper treatment of nonorthogonality in the space of single excitations and invokes, when necessary, a constrained optimization procedure to prevent the variational collapse of excited states. In addition, a configuration selection scheme (suitable for use in conjunction with extended configuration interaction methods) is proposed for the MCSCF procedure. The algorithm is used to study the low-lying singlet states of BeO, a system which has not previously been studied using an MCSCF procedure. MCSCF wave functions are obtained for three 1 Sigma + and two 1 Pi states. The 1 Sigma + results are juxtaposed with comparable results for MgO in order to assess the generality of the description presented here.
In order to understand the seemingly erratic V/R variations and radial velocity curves of emission edges and central absorption of some Be stars, a theory is advanced to explain the changes of structure of the gaseous ring around these stars. The theory is based on the interaction between the existing ring and the newly ejected matter from the star. It shows that the structural change of the ring is completely controlled by the angular momentum input factor and the dissipation factor. In light of this understanding, the observed results of beta Mon and Pi Aqr. are interpreted.
One-dimensional hybrid computer simulations that are spatially homogeneous are used to investigate the evolution of newborn cometary ions that interact self-consistently with the solar wind. Cometary ions injected at a constant rate are scattered by the growing electromagnetic fluctuations resulting from the associated free energy, and the scattering at relatively low fluctuating field amplitudes leads to shell-like velocity distributions which subtend about 4 pi in solid angle but which have small spread in speed. Shell-like distributions are found to occur when the ion injection rate is relatively slow, when the injected ion mass is relatively light, and when the energy density of the fluctuating magnetic fields exhibits linear growth.
For the meeting of the AAS/SPD in Albuquerque, NM, I organized a Topical Session of the AAS on Structure and Dynamics of Chromospheres. The grant support was used to bring to the US two of the speakers from abroad. I had invited them for presentations at the Session: Dr. Klaus Wilhelm, the former PI of the SUMER instrument on SOHO, from the Max-Planck Institut in Lindau, Germany, and Dr. Sirajul Hasan, from the Indian Institute of Astrophysics in Bangalore, India. Both speakers preceded their trip to the AAS meeting with a stay at the Smithsonian Astrophysical Observatory, where they interacted with members of the Solar and Stellar Physics division. The highlights of the visits were the talks at the AAS/SPD meeting, in which six invited speakers told the audience of astronomers about current problems in solar physics and their relation to stellar problems. An important result of the visits is a paper by Dr. Wilhelm and me on 'Observations of the upper solar chromosphere with SUMER on SOHO', which has been submitted to Astronomy and Astrophysics for publication.
The distribution of insoluble particles in a metal casting depends primarily on the interaction of the particles with the solid/liquid interface (SLI) during the solidification process. Whether a particle will be engulfed or continuously pushed by SLI is essentially determined by the balance of forces acting on the particle. An important component of this force balance is the drag force generated by the particle motion in front of the SLI. Previously developed mathematical models for particle/SLI interaction made use of steady-state solutions of this force provided by the lubrication theory. However, our numerical model based on the SLI tracking approach shows that not only the steady-state approach is inappropriate to model the interaction process but also that even at steady-state the theoretical solution underestimates the drag force. A regression analysis of steady-state numerical solutions for cylindrical particles moving normal to a flat SLI gave a relationship of the form F(sub d) (exp num) = (square root of 3) pi eta V(sub p)((R(sub p) / d) (exp 10 gamma/3)) as compared to the theoretical solution F(sub d) (exp theor) = 3 X (square root of 2) pi eta V(sub p)((R(sub p) / d) (exp 3/2)) where F(sub d) is the drag force, eta is the dynamic viscosity of the fluid, V(sub p) is the particle velocity, R(sub p) is the particle radius, gamma is Euler's constant (gamma is approximately equal to 0.577), and d is the width of the gap between the particle and the SLI. Model validation as well as the influence of the interface shape on the value of F(sub d) will also be discussed.
The distribution of insoluble particles in a metal casting depends primarily on the interaction of the particles with the solid/liquid interface (SLI) during the solidification process. The balance of the forces acting on the particle essentially determines whether a particle will be engulfed or pushed by the SLI. An important component of this force balance is the drag force generated by the particle motion in front of the SLI. Previously developed mathematical models for particle/SLI interaction made use of steady-state solutions of this force provided by the lubrication theory. However, our numerical model based on the SLI tracking approach shows that the steady-state approach is inappropriate to model the interaction process and that at steady-state the theoretical solution underestimates the drag force. It was found that regression analysis of steady-state numerical solutions for cylindrical particles moving normal to a flat SLI gives a relationship of the form: Abstract The distribution of insoluble particles in a metal casting depends primarily on the interaction of the particles with the solid/liquid interface (SLI) during the solidification process. The balance of the forces acting on the particle essentially determines whether a particle will be engulfed or pushed by the SLI. An important component of this force balance is the drag force generated by the particle motion in front of the SLI. Previously developed mathematical models for particle/SLI interaction made use of steady-state solutions of this force provided by the lubrication theory. However, our numerical model based on the SLI tracking approach shows that the steady-state approach is inappropriate to model the interaction process and that at steady-state the theoretical solution underestimates the drag force. It was found that regression analysis of steady-state numerical solutions for cylindrical particles moving normal to a flat SLI gives a relationship of the form: F(sub D, sup num) =sqoare root of 3(pi)(eta)V(sub p)(R(sub p)/d)(sup 10(gamma)/3). This is to compared to the solution provided by the lubrication theory: F(sub D), sup theor) = 3 square root of 2(pi)(eta)V(sub p)(R(sub p)/d)(sub 3/2), where F(sub D) is the drag force, eta is the dynamic viscosity of the fluid, V(sub p) is the particle velocity, R(sub p) is the particle radius, gamma is Euler's constant (gamma approx. = 0.577), and d is the width of the gap between the particle and the SLI. The domain on which the equations proposed by the lubrication theory are relevant is clearly identified in the paper. The numerical model was then validated against the classical lubrication theory within the domain of its validity.
Theoretical dissociation energies for the ground states of the alkali and alkaline earth oxides are presented that are believed to be accurate to 0.1 eV. The 2 Pi - 2 Sigma + separations for the alkali oxides are found to be more sensitive to basis set than to electron correlation. Predicted 2 Pi ground states for LiO and NaO and 2 Sigma + ground states for RbO and CsO are found to be in agreement with previous theoretical and experimental work. For KO, a 2 Sigma + state is found at both the numerical Hartree-Fock (NHF) level and at the singles plus doubles configuration interaction level using a Slater basis set that is within 0.02 eV of the NHF limit. It is found that an accurate balanced treatment of the two states requires correlating the electrons on both the metal and oxide ion.
In order to understand the seemingly erratic V/R variations and radial velocity curves of emission edges and central absorption of some Be stars, we have advanced, for the changes of structure of the gaseous ring around these stars, a theory that is based on the interaction between the existing ring and the newly ejected matter from the star. It shows that the structural change of the ring is completely controlled by the angular-momentum input factor and the dissipation factor. In light of this understanding, we have gone on to interpret the observed results of Beta-1 Mon and Pi Aqr.
The interaction of La(+) and La(2+) with C2H2, C2H4, and C3H6 is studied using electronic structure calculations that include correlation. The calculations show that the bonding in the dication is electrostatic in origin, and the computed binding energies are in good agreement with experiment. The La(+) forms two chemical bonds with the hydrocarbons. Since the pi bond is weaker for C2H2 than C2H4, the La(+)-C2H2 binding energy is larger than for La(+)-C2H4, LaC3H6(+) rearranges to yield a stronger bond than in LaC2H4(+) even though both hydrocarbons have a double bond.
Eight surrogate spaceflight mission specialists participated in a real-time evaluation of remote coaching using the Ames Life Science Telescience Testbed facility. This facility consisted of three remotely located nodes: (1) a prototype Space Station glovebox; (2) a ground control station; and (3) a principal investigator's (PI) work area. The major objective of this project was to evaluate the effectiveness of telescience techniques and hardware to support three realistic remote coaching science procedures: plant seed germinator charging, plant sample acquisition and preservation, and remote plant observation with ground coaching. Each scenario was performed by a subject acting as flight mission specialist, interacting with a payload operations manager and a principal investigator expert. All three groups were physically isolated from each other yet linked by duplex audio and color video communication channels and networked computer workstations. Workload ratings were made by the flight and ground crewpersons immediately after completing their assigned tasks. Time to complete each scientific procedural step was recorded automatically. Two expert observers also made performance ratings and various error assessments. The results are presented and discussed.
We propose a combined Titan orbiter and Titan Aerorover mission with an emphasis on both in situ and remote sensing measurements of Titan's surface, atmosphere, ionosphere, and magnetospheric interaction. The biological aspect of the Titan environment will be emphasized by the mission (i.e., search for organic materials which may include simple organics to 'amono' analogues of amino acids and possibly more complex, lightening detection and infrared, ultraviolet, and charged particle interactions with Titan's surface and atmosphere). An international mission is assumed to control costs. NASA will provide the orbiter, launch vehicle, DSN coverage and operations, while international partners will provide the Aerorover and up to 30% of the cost for the scientific instruments through collaborative efforts. To further reduce costs we propose a single PI for orbiter science instruments and a single PI for Aerorover science instruments. This approach will provide single command/data and power interface between spacecraft and orbiter instruments that will have redundant central DPU and power converter for their instruments. A similar approach could be used for the Aerorover. The mission profile will be constructed to minimize conflicts between Aerorover science, orbiter radar science, orbiter radio science, orbiter imaging science, and orbiter fields and particles (FP) science. Additional information is contained in the original extended abstract.
We interfaced a Hot-Filament Chemical Vapor Deposition (HFCVD) system to the emission port of an FT-IR spectrometer, in order to study the gas phase species present during the deposition of diamond thin films. The implementation of the infrared (IR) emission technique in situ allowed the study of various carbon-containing species believed to be crucial in diamond film growth. The two IR-active vibrational fundamentals of methane, v(3)(f2) and v(4)(f2), were observed at three different filament temperatures: 1000, 1500 and 2000 C. However, the net signal of v(3) was emission, while that of v(4) was absorption. These results indicate that the v(4) fundamental is excited beyond equilibrium, while the v(3) fundamental remains mostly in the ground state. This is due to the small concentration of methane, the low energy of v(4) compared to v(3) or to the Hz vibrational mode, and symmetry considerations that forbid interaction among the four fundamentals of methane. Thus, the excitation of v(3) is more likely than its decay under HFCVD conditions, producing a non-equilibrium population. At a filament temperature of 2000 C, the v(3) (sigma(+)(3)) fundamental of acetylene and a band at 1328 cm-l also ascribed to acetylene (v5 (pi(U)) + v4) appear in net absorption. This correlates well with the onset of molecular hydrogen breaking by the filament, which occurs at temperatures around 2000 C and above. The hydrogen atoms produced in this heterogeneous reaction give rise to a chain of reactions that lead to acetylene, among other carbonaceous species.
The interaction of the Sc and Y singly-charged and dipositive ions with C2H2, C2H4, and C3H6 is studied using electronic structure calculations that include high levels of electron correlation. These results are compared with comparable calculations performed previously for La(+) and La(2+). For C2H2 and C2H4, all three metal ions insert into the C-C pi bond, making a three-membered ring. The optimal structures for the MC3H6(+) ions all involve rearrangement to make a four-membered ring. The strength of the metal-ligand bond for the singly charged ions follows the order La greater than Sc equal to about Y. In contrast, the bonds involving the dipositive ions are electrostatic, so that the binding energy increases as the size of the ion decreases, leading to the trend Sc greater than Y greater than La.
As a theoretical component of the joint effort with the laboratory of Dr. Lou Allamandola to search for potential candidates for interstellar organic carbon compound that are responsible for the visible diffuse interstellar absorption bands (DIB's), quantum mechanical calculations were performed on the electron absorption spectra of selected polycyclic aromatic hydrocarbons (PAH) and derivatives. In the completed project, 15 different species of naphthalene, its hydrogen abstraction and addition derivatives, and corresponding cations and anions were studied. Using semiempirical quantum mechanical method INDO/S, the ground electronic state of each species was evaluated with restricted Hartree-Fock scheme and limited configuration interaction. The lowest energy spin state for each species was used for electron absorption calculations. Results indicate that these calculations are accurate enough to reproduce the spectra of naphthalene cation and anion observed in neon matrix. The spectral pattern of the hydrogen abstraction and addition derivatives predicted based on these results indicate that the electron configuration of the pi orbitals of these species is the dominant determinant. A combined list of 19 absorptions calculated from 4500 A to 10,400 A were compiled and suggested as potential candidates that are relevant for the DIB's absorptions. Continued studies on pyrene and derivatives revealed the ground state symmetries and multiplicities of its neutral, anionic, and cationic species. Spectral calculations show that the cation (B(sub 3g)-2) and the anion (A(sub u)-2) are more likely to have low energy absorptions in the regions between 10 kK and 20 kK, similar to naphthalene. These absorptions, together with those to be determined from the hydrogen abstraction and addition derivatives of pyrene, can be used to provide additional candidates and suggest experimental work in the search for interstellar compounds that are responsible for DIB's.