Manipulating localized molecular orbitals by single-atom contacts.

Science.gov (United States)

Wang, Weihua; Shi, Xingqiang; Lin, Chensheng; Zhang, Rui Qin; Minot, Christian; Van Hove, Michel A; Hong, Yuning; Tang, Ben Zhong; Lin, Nian

2010-09-17

We have fabricated atom-molecule contacts by attachment of single Cu atoms to terpyridine side groups of bis-terpyridine tetra-phenyl ethylene molecules on a Cu(111) surface. By means of scanning tunneling microscopy, spectroscopy, and density functional calculations, we have found that, due to the localization characteristics of molecular orbitals, the Cu-atom contact modifies the state localized at the terpyridine side group which is in contact with the Cu atom but does not affect the states localized at other parts of the molecule. These results illustrate the contact effects at individual orbitals and offer possibilities to manipulate orbital alignments within molecules.

On the physical interpretation of the nuclear molecular orbital energy.

Science.gov (United States)

Charry, Jorge; Pedraza-González, Laura; Reyes, Andrés

2017-06-07

Recently, several groups have extended and implemented molecular orbital (MO) schemes to simultaneously obtain wave functions for electrons and selected nuclei. Many of these schemes employ an extended Hartree-Fock approach as a first step to find approximate electron-nuclear wave functions and energies. Numerous studies conducted with these extended MO methodologies have explored various effects of quantum nuclei on physical and chemical properties. However, to the best of our knowledge no physical interpretation has been assigned to the nuclear molecular orbital energy (NMOE) resulting after solving extended Hartree-Fock equations. This study confirms that the NMOE is directly related to the molecular electrostatic potential at the position of the nucleus.

Molecular integrals for slater type orbitals using coulomb sturmians

DEFF Research Database (Denmark)

Avery, James Emil; Avery, John Scales

2014-01-01

The use of Slater type orbitals in molecular calculations is hindered by the slowness of integral evaluation. In the present paper, we introduce a method for overcoming this problem by expanding STO's in terms of Coulomb Sturmians, for which the problem of evaluating molecular integrals rapidly has...

Destructive quantum interference in electron transport: A reconciliation of the molecular orbital and the atomic orbital perspective

Science.gov (United States)

Zhao, Xin; Geskin, Victor; Stadler, Robert

2017-03-01

Destructive quantum interference (DQI) in single molecule electronics is a purely quantum mechanical effect and is entirely defined by the inherent properties of the molecule in the junction such as its structure and symmetry. This definition of DQI by molecular properties alone suggests its relation to other more general concepts in chemistry as well as the possibility of deriving simple models for its understanding and molecular device design. Recently, two such models have gained a wide spread attention, where one was a graphical scheme based on visually inspecting the connectivity of the carbon sites in conjugated π systems in an atomic orbital (AO) basis and the other one puts the emphasis on the amplitudes and signs of the frontier molecular orbitals (MOs). There have been discussions on the range of applicability for these schemes, but ultimately conclusions from topological molecular Hamiltonians should not depend on whether they are drawn from an AO or a MO representation, as long as all the orbitals are taken into account. In this article, we clarify the relation between both models in terms of the zeroth order Green's function and compare their predictions for a variety of systems. From this comparison, we conclude that for a correct description of DQI from a MO perspective, it is necessary to include the contributions from all MOs rather than just those from the frontier orbitals. The cases where DQI effects can be successfully predicted within a frontier orbital approximation we show them to be limited to alternant even-membered hydrocarbons, as a direct consequence of the Coulson-Rushbrooke pairing theorem in quantum chemistry.

Assessing the Bonding Properties of Individual Molecular Orbitals

OpenAIRE

Robinson, PJ; Alexandrova, AN

2015-01-01

© 2015 American Chemical Society. Molecular orbitals (MOs), while one of the most widely used representations of the electronic structure of a system, are often too complex to intuit properties. Aside from the simplest of cases, it is not necessarily possible to visually tell which orbitals are bonding or antibonding along particular directions, especially in cases of highly delocalized and nontrivial bonding like metal clusters or solids. We propose a method for easily assessing and comparin...

Development of the Fragment Molecular Orbital Method for Calculating Nonlocal Excitations in Large Molecular Systems.

Science.gov (United States)

Fujita, Takatoshi; Mochizuki, Yuji

2018-04-19

We developed the fragment-based method for calculating nonlocal excitations in large molecular systems. This method is based on the multilayer fragment molecular orbital method and the configuration interaction single (CIS) wave function using localized molecular orbitals. The excited-state wave function for the whole system is described as a superposition of configuration state functions (CSFs) for intrafragment excitations and for interfragment charge-transfer excitations. The formulation and calculations of singlet excited-state Hamiltonian matrix elements in the fragment CSFs are presented in detail. The efficient approximation schemes for calculating the matrix elements are also presented. The computational efficiency and the accuracy were evaluated using the molecular dimers and molecular aggregates. We confirmed that absolute errors of 50 meV (relative to the conventional calculations) are achievable for the molecular systems in their equilibrium geometries. The perturbative electron correlation correction to the CIS excitation energies is also demonstrated. The present theory can compute a large number of excited states in large molecular systems; in addition, it allows for the systematic derivation of a model exciton Hamiltonian. These features are useful for studying excited-state dynamics in condensed molecular systems based on the ab initio electronic structure theory.

Equation of state of dense plasmas: Orbital-free molecular dynamics as the limit of quantum molecular dynamics for high-Z elements

Energy Technology Data Exchange (ETDEWEB)

Danel, J.-F.; Blottiau, P.; Kazandjian, L.; Piron, R.; Torrent, M. [CEA, DAM, DIF, 91297 Arpajon (France)

2014-10-15

The applicability of quantum molecular dynamics to the calculation of the equation of state of a dense plasma is limited at high temperature by computational cost. Orbital-free molecular dynamics, based on a semiclassical approximation and possibly on a gradient correction, is a simulation method available at high temperature. For a high-Z element such as lutetium, we examine how orbital-free molecular dynamics applied to the equation of state of a dense plasma can be regarded as the limit of quantum molecular dynamics at high temperature. For the normal mass density and twice the normal mass density, we show that the pressures calculated with the quantum approach converge monotonically towards those calculated with the orbital-free approach; we observe a faster convergence when the orbital-free approach includes the gradient correction. We propose a method to obtain an equation of state reproducing quantum molecular dynamics results up to high temperatures where this approach cannot be directly implemented. With the results already obtained for low-Z plasmas, the present study opens the way for reproducing the quantum molecular dynamics pressure for all elements up to high temperatures.

Spectral properties of minimal-basis-set orbitals: Implications for molecular electronic continuum states

Science.gov (United States)

Langhoff, P. W.; Winstead, C. L.

Early studies of the electronically excited states of molecules by John A. Pople and coworkers employing ab initio single-excitation configuration interaction (SECI) calculations helped to simulate related applications of these methods to the partial-channel photoionization cross sections of polyatomic molecules. The Gaussian representations of molecular orbitals adopted by Pople and coworkers can describe SECI continuum states when sufficiently large basis sets are employed. Minimal-basis virtual Fock orbitals stabilized in the continuous portions of such SECI spectra are generally associated with strong photoionization resonances. The spectral attributes of these resonance orbitals are illustrated here by revisiting previously reported experimental and theoretical studies of molecular formaldehyde (H2CO) in combination with recently calculated continuum orbital amplitudes.

Molecular models of zinc phthalocyanines: semi-empirical molecular orbital computations and physicochemical properties studied by molecular mechanics simulations

International Nuclear Information System (INIS)

Gantchev, Tsvetan G.; van Lier, Johan E.; Hunting, Darel J.

2005-01-01

To build 3D-molecular models of Zinc-phthalocyanines (ZnPc) and to study their diverse chemical and photosensitization properties, we performed quantum mechanical molecular orbital (MO) semi-empirical (AM1) computations of the ground, excited singlet and triplet states as well as free radical (ionic) species. RHF and UHF (open shell) geometry optimizations led to near-perfect symmetrical ZnPc. Predicted ionization potentials (IP), electron affinities (EA) and lowest electronic transitions of ZnPc are in good agreement with the published experimental and theoretical data. The computation-derived D 4h /D 2h -symmetry 3D-structures of ground and excited states and free radicals of ZnPc, together with the frontier orbital energies and Mulliken electron population analysis enabled us to build robust molecular models. These models were used to predict important chemical-reactivity entities such as global electronegativity (χ), hardness (η) and local softness based on Fukui-functions analysis. Examples of molecular mechanics (MM) applications of the 3D-molecular models are presented as approaches to evaluate solvation free energy (ΔG 0 ) solv and to estimate ground- and excited- state oxidation/reduction potentials as well as intermolecular interactions and stability of ground and excited state dimers (exciplexes) and radical ion-pairs

Field theoretic approach to dynamical orbital localization in ab initio molecular dynamics

International Nuclear Information System (INIS)

Thomas, Jordan W.; Iftimie, Radu; Tuckerman, Mark E.

2004-01-01

Techniques from gauge-field theory are employed to derive an alternative formulation of the Car-Parrinello ab initio molecular-dynamics method that allows maximally localized Wannier orbitals to be generated dynamically as the calculation proceeds. In particular, the Car-Parrinello Lagrangian is mapped onto an SU(n) non-Abelian gauge-field theory and the fictitious kinetic energy in the Car-Parrinello Lagrangian is modified to yield a fully gauge-invariant form. The Dirac gauge-fixing method is then employed to derive a set of equations of motion that automatically maintain orbital locality by restricting the orbitals to remain in the 'Wannier gauge'. An approximate algorithm for integrating the equations of motion that is stable and maintains orbital locality is then developed based on the exact equations of motion. It is shown in a realistic application (64 water molecules plus one hydrogen-chloride molecule in a periodic box) that orbital locality can be maintained with only a modest increase in CPU time. The ability to keep orbitals localized in an ab initio molecular-dynamics calculation is a crucial ingredient in the development of emerging linear scaling approaches

Molecular orbital study of the chemisorption of carbon monoxide on a tungsten (100) surface

International Nuclear Information System (INIS)

Lee, T.H.; Rabalais, J.W.

1978-01-01

The adsorption energies of carbon monoxide chemisorbed at various sites on a tungsten (100) surface have been calculated by extended Hueckel molecular orbital theory (EHMO). The concept of a 'surface molecule' in which CO is bonded to an array of tungsten atoms Wsub(n) has been employed. Dissociative adsorption in which C occupies a four-fold, five-coordination site and O occupies either a four- or two-fold site has been found to be the most stable form for CO on a W surface. Stable one-fold and two-fold sites of molecularly adsorbed CO have also been found in which the CO group is normal to the surface plane and the C atom is nearest the surface. Adsorption energies and molecular orbitals for the stable molecularly and dissociatively adsorbed CO sites are compared with the experimental data on various types of adsorbed CO, i.e. virgin-, α-, and β-CO. Models are suggested for each of these adsorption types. The strongest bonding interactions occur between the CO 5sigma orbital and the totally symmetric 5d and 6s orbitals of the Wsub(n) cluster. Possible mechanisms for conversion of molecularly adsorbed CO to dissociatively adsorbed CO are proposed and the corresponding activation energies are estimated. (Auth.)

Finite-temperature orbital-free DFT molecular dynamics: Coupling PROFESS and QUANTUM ESPRESSO

Science.gov (United States)

Karasiev, Valentin V.; Sjostrom, Travis; Trickey, S. B.

2014-12-01

Implementation of orbital-free free-energy functionals in the PROFESS code and the coupling of PROFESS with the QUANTUM ESPRESSO code are described. The combination enables orbital-free DFT to drive ab initio molecular dynamics simulations on the same footing (algorithms, thermostats, convergence parameters, etc.) as for Kohn-Sham (KS) DFT. All the non-interacting free-energy functionals implemented are single-point: the local density approximation (LDA; also known as finite-T Thomas-Fermi, ftTF), the second-order gradient approximation (SGA or finite-T gradient-corrected TF), and our recently introduced finite-T generalized gradient approximations (ftGGA). Elimination of the KS orbital bottleneck via orbital-free methodology enables high-T simulations on ordinary computers, whereas those simulations would be costly or even prohibitively time-consuming for KS molecular dynamics (MD) on very high-performance computer systems. Example MD simulations on H over a temperature range 2000 K ≤ T ≤4,000,000 K are reported, with timings on small clusters (16-128 cores) and even laptops. With respect to KS-driven calculations, the orbital-free calculations are between a few times through a few hundreds of times faster.

Emulating Molecular Orbitals and Electronic Dynamics with Ultracold Atoms

Directory of Open Access Journals (Sweden)

Dirk-Sören Lühmann

2015-08-01

Full Text Available In recent years, ultracold atoms in optical lattices have proven their great value as quantum simulators for studying strongly correlated phases and complex phenomena in solid-state systems. Here, we reveal their potential as quantum simulators for molecular physics and propose a technique to image the three-dimensional molecular orbitals with high resolution. The outstanding tunability of ultracold atoms in terms of potential and interaction offer fully adjustable model systems for gaining deep insight into the electronic structure of molecules. We study the orbitals of an artificial benzene molecule and discuss the effect of tunable interactions in its conjugated π electron system with special regard to localization and spin order. The dynamical time scales of ultracold atom simulators are on the order of milliseconds, which allows for the time-resolved monitoring of a broad range of dynamical processes. As an example, we compute the hole dynamics in the conjugated π system of the artificial benzene molecule.

Generalized molecular orbital theory: a limited multiconfiguration self-consistent-field-theory

International Nuclear Information System (INIS)

Hall, M.B.

1981-01-01

The generalized molecular orbital (GMO) approach is a limited type of multiconfiguration self-consistent-field (MCSCF) calculation which divides the orbitals of a closed shell molecule into four shells: doubly occupied, strongly occupied, weakly occupied, and unoccupied. The orbitals within each shell have the same occupation number and are associated with the same Fock operator. Thus, the orbital optimization is ideally suited to solution via a coupling operator. The determination of the orbitals is followed by a configuration interaction (CI) calculation within the strongly and weakly occupied shells. Results for BH 3 show a striking similarity between the GMO's and the natural orbitals (NO's) from an all singles and doubles CI calculation. Although the GMO approach would not be accurate for an entire potential surface, results for spectroscopic constants of N 2 show that it is suitable near the equilibrium geometry. This paper describes the use of the GMO technique to determine the primary orbital space, but a potentially important application may be in the determination of a secondary orbital space following a more accurate MCSCF determination of the primary space

Orbital free molecular dynamics; Approche sans orbitale des plasmas denses

Energy Technology Data Exchange (ETDEWEB)

Lambert, F

2007-08-15

The microscopic properties of hot and dense plasmas stay a field essentially studied thanks to classical theories like the One Component Plasma, models which rely on free parameters, particularly ionization. In order to investigate these systems, we have used, in this PhD work, a semi-classical model, without free parameters, that is based on coupling consistently classical molecular dynamics for the nuclei and orbital free density functional theory for the electrons. The electronic fluid is represented by a free energy entirely determined by the local density. This approximation was validated by a comparison with an ab initio technique, quantum molecular dynamics. This one is identical to the previous except for the description of the free energy that depends on a quantum-independent-particle model. Orbital free molecular dynamics was then used to compute equation of state of boron and iron plasmas in the hot and dense regime. Furthermore, comparisons with classical theories were performed on structural and dynamical properties. Finally, equation of state and transport coefficients mixing laws were studied by direct simulation of a plasma composed of deuterium and copper. (author)

Fundamentals of quantum chemistry

CERN Document Server

House, J E

2004-01-01

An introduction to the principles of quantum mechanics needed in physical chemistry. Mathematical tools are presented and developed as needed and only basic calculus, chemistry, and physics is assumed. Applications include atomic and molecular structure, spectroscopy, alpha decay, tunneling, and superconductivity. New edition includes sections on perturbation theory, orbital symmetry of diatomic molecules, the Huckel MO method and Woodward/Hoffman rules as well as a new chapter on SCF and Hartree-Fock methods. * This revised text clearly presents basic q

A brief introduction to molecular orbital theory of simple polyatomic molecules for undergraduate chemistry students

Directory of Open Access Journals (Sweden)

Ione M. Baibich

2012-01-01

Full Text Available A simple, four-step method for better introducing undergraduate students to the fundamentals of molecular orbital (MO theory of the polyatomic molecules H2O, NH3, BH3 and SiH4 using group theory is reported. These molecules serve to illustrate the concept of ligand group orbitals (LGOs and subsequent construction of MO energy diagrams on the basis of molecular symmetry requirements.

[OsF6]x−: Molecular Models for Spin-Orbit Entangled Phenomena

DEFF Research Database (Denmark)

Pedersen, Kasper Steen; Woodruff, Daniel N.; Singh, Saurabh Kumar

2017-01-01

Heavy 5d elements, like osmium, feature strong spin-orbit interactions which are at the origin of exotic physical behaviors. Revealing the full potential of, for example, novel osmium oxide materials (“osmates”) is however contingent upon a detailed understanding of the local single-ion propertie...... state was elucidated; mirroring the osmium electronic structure in osmates. The realization of such molecular model systems provides a unique chemical playground to engineer materials exhibiting spin-orbit entangled phenomena....

Tuning the effective spin-orbit coupling in molecular semiconductors

KAUST Repository

Schott, Sam

2017-05-11

The control of spins and spin to charge conversion in organics requires understanding the molecular spin-orbit coupling (SOC), and a means to tune its strength. However, quantifying SOC strengths indirectly through spin relaxation effects has proven difficult due to competing relaxation mechanisms. Here we present a systematic study of the g-tensor shift in molecular semiconductors and link it directly to the SOC strength in a series of high-mobility molecular semiconductors with strong potential for future devices. The results demonstrate a rich variability of the molecular g-shifts with the effective SOC, depending on subtle aspects of molecular composition and structure. We correlate the above g-shifts to spin-lattice relaxation times over four orders of magnitude, from 200 to 0.15 μs, for isolated molecules in solution and relate our findings for isolated molecules in solution to the spin relaxation mechanisms that are likely to be relevant in solid state systems.

Tuning the effective spin-orbit coupling in molecular semiconductors

KAUST Repository

Schott, Sam; McNellis, Erik R.; Nielsen, Christian B.; Chen, Hung-Yang; Watanabe, Shun; Tanaka, Hisaaki; McCulloch, Iain; Takimiya, Kazuo; Sinova, Jairo; Sirringhaus, Henning

2017-01-01

The control of spins and spin to charge conversion in organics requires understanding the molecular spin-orbit coupling (SOC), and a means to tune its strength. However, quantifying SOC strengths indirectly through spin relaxation effects has proven difficult due to competing relaxation mechanisms. Here we present a systematic study of the g-tensor shift in molecular semiconductors and link it directly to the SOC strength in a series of high-mobility molecular semiconductors with strong potential for future devices. The results demonstrate a rich variability of the molecular g-shifts with the effective SOC, depending on subtle aspects of molecular composition and structure. We correlate the above g-shifts to spin-lattice relaxation times over four orders of magnitude, from 200 to 0.15 μs, for isolated molecules in solution and relate our findings for isolated molecules in solution to the spin relaxation mechanisms that are likely to be relevant in solid state systems.

Fulde-Ferrell-Like Molecular States in Spin-Orbit Coupled Ultracold Fermi Gases

Science.gov (United States)

Ye, Chong; Fu, Li-Bin

2017-08-01

We study the molecular state in three-component Fermi gases with a single impurity of 6 Li immersing in a no-interacting Fermi sea of 40 K in the presence of an equal weight combination of Rashba-type and Dresselhaus-type spin-orbit coupling. In the region where the Fermi sea has two disjointed Fermi surfaces, we find that there are two Fulde-Ferrell-like molecular states with dominating contributions from the lower helicity branch. Decreasing the scattering length or the spin-orbit coupled Fermi energy, we find the Fulde-Ferrell-like molecular state with small center-of-mass momentum is always energy favored and the other one will suddenly disappear. Supported by the National Basic Research Program of China (973 Program) under Grant Nos. 2013CBA01502, 2013CB834100, and the National Natural Science Foundation of China under Grant Nos. 11374040, 11475027, 11575027, 11274051, and 11075020

Electronic structure and molecular orbital study of hole-transport material triphenylamine derivatives

International Nuclear Information System (INIS)

Wang, B.-C.; Liao, H.-R.; Chang, J.-C.; Chen Likey; Yeh, J.-T.

2007-01-01

Recently, triphenylamine (TPA), 4,4'-bis(phenyl-m-tolylamino)biphenyl (TPD), 4,4'-bis(1-naphthylphenylamino)biphenyl (NPB) and their derivatives are widely used in the organic light-emitting diode (OLED) devices as a hole-transporting material (HTM) layer. We have optimized twenty different structures of HTM materials by using density functional theory (DFT), B3LYP/6-31G method. All these different structures contain mono-amine and diamine TPA derivatives. The energies of highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) along with molecular orbitals for these HTMs are also determined. We have found that the central amine nitrogen atom and the phenyl ring, which is next to the central amine nitrogen atom, show significant contribution to the HOMO and LUMO, respectively. The sum of the calculated bond angles (α+β+γ) of the central amine nitrogen atom has been applied to describe the bonding and the energy difference for HOMO and LUMO in these TPA derivatives. Electronic structure calculations have been performed for these TPA derivatives. Again, the LCAO-MO patterns of HOMO and LUMO levels of these derivatives are used to investigate their electron density. A series of electron-transporting steps are predicted for these compounds employing these calculated results

Laplace-transformed multi-reference second-order perturbation theories in the atomic and active molecular orbital basis

NARCIS (Netherlands)

Helmich-Paris, B.; Knecht, Stefan

2017-01-01

In the present article, we show how to formulate the partially contracted n-electron valence second-order perturbation theory (NEVPT2) energies in the atomic and active molecular orbital basis by employing the Laplace transformation of orbital-energy denominators (OEDs). As atomic-orbital (AO) basis

The spectral distribution of intermediate L-K molecular-orbital radiation in symmetric heavy-ion collisions

International Nuclear Information System (INIS)

Heinig, K.-H.; Jager, H.-U.; Richter, H.; Woittennek, H.; Frank, W.; Gippener, P.; Kaun, K.-H.; Manfrass, P.

1977-01-01

Two distinct x-ray continua C1 and C2 above the characteristic lines are observed in high-energy collisions between atoms with atomic numbers of 28 to 57. This structure is explained by a superposition of K molecular-orbital (KMO) radiation and of an intermediate L-K molecular-orbital (ILKMO) radiation of high intensity which is due to 2psigma vacancies. In the framework of the dynamical theory of intermediate molecular phenomena and using a scaling of the H 2 + correlation diagram with screened state-dependent charges good agreement between the shapes of the measured and calculated spectra is obtained. (author)

GAUSSIAN 76: an ab initio molecular orbital program

International Nuclear Information System (INIS)

Binkley, J.S.; Whiteside, R.; Hariharan, P.C.; Seeger, R.; Hehre, W.J.; Lathan, W.A.; Newton, M.D.; Ditchfield, R.; Pople, J.A.

Gaussian 76 is a general-purpose computer program for ab initio Hartree-Fock molecular orbital calculations. It can handle basis sets involving s, p and d-type gaussian functions. Certain standard sets (STO-3G, 4-31G, 6-31G*, etc.) are stored internally for easy use. Closed shell (RHF) or unrestricted open shell (UHF) wave functions can be obtained. Facilities are provided for geometry optimization to potential minima and for limited potential surface scans

Physical Meaning of Virtual Kohn-Sham Orbitals and Orbital Energies: An Ideal Basis for the Description of Molecular Excitations.

Science.gov (United States)

van Meer, R; Gritsenko, O V; Baerends, E J

2014-10-14

In recent years, several benchmark studies on the performance of large sets of functionals in time-dependent density functional theory (TDDFT) calculations of excitation energies have been performed. The tested functionals do not approximate exact Kohn-Sham orbitals and orbital energies closely. We highlight the advantages of (close to) exact Kohn-Sham orbitals and orbital energies for a simple description, very often as just a single orbital-to-orbital transition, of molecular excitations. Benchmark calculations are performed for the statistical average of orbital potentials (SAOP) functional for the potential [J. Chem. Phys. 2000, 112, 1344; 2001, 114, 652], which approximates the true Kohn-Sham potential much better than LDA, GGA, mGGA, and hybrid potentials do. An accurate Kohn-Sham potential does not only perform satisfactorily for calculated vertical excitation energies of both valence and Rydberg transitions but also exhibits appealing properties of the KS orbitals including occupied orbital energies close to ionization energies, virtual-occupied orbital energy gaps very close to excitation energies, realistic shapes of virtual orbitals, leading to straightforward interpretation of most excitations as single orbital transitions. We stress that such advantages are completely lost in time-dependent Hartree-Fock and partly in hybrid approaches. Many excitations and excitation energies calculated with local density, generalized gradient, and hybrid functionals are spurious. There is, with an accurate KS, or even the LDA or GGA potentials, nothing problematic about the "band gap" in molecules: the HOMO-LUMO gap is close to the first excitation energy (the optical gap).

Automated Construction of Molecular Active Spaces from Atomic Valence Orbitals.

Science.gov (United States)

Sayfutyarova, Elvira R; Sun, Qiming; Chan, Garnet Kin-Lic; Knizia, Gerald

2017-09-12

We introduce the atomic valence active space (AVAS), a simple and well-defined automated technique for constructing active orbital spaces for use in multiconfiguration and multireference (MR) electronic structure calculations. Concretely, the technique constructs active molecular orbitals capable of describing all relevant electronic configurations emerging from a targeted set of atomic valence orbitals (e.g., the metal d orbitals in a coordination complex). This is achieved via a linear transformation of the occupied and unoccupied orbital spaces from an easily obtainable single-reference wave function (such as from a Hartree-Fock or Kohn-Sham calculations) based on projectors to targeted atomic valence orbitals. We discuss the premises, theory, and implementation of the idea, and several of its variations are tested. To investigate the performance and accuracy, we calculate the excitation energies for various transition-metal complexes in typical application scenarios. Additionally, we follow the homolytic bond breaking process of a Fenton reaction along its reaction coordinate. While the described AVAS technique is not a universal solution to the active space problem, its premises are fulfilled in many application scenarios of transition-metal chemistry and bond dissociation processes. In these cases the technique makes MR calculations easier to execute, easier to reproduce by any user, and simplifies the determination of the appropriate size of the active space required for accurate results.

Peptide Free Energy Landscapes Calibrated by Molecular Orbital Calculations

OpenAIRE

Ono, S.; Kuroda, M.; Higo, J.; Kamiya, N.; Nakajima, N.; Nakamura, H.

2002-01-01

Free energy landscapes of peptide conformations werecalibrated by ab initiomolecular orbital calculations, after enhancedconformational sampling using the multicanonical molecular dynamicssimulations. Three different potentials of mean force for an isolateddipeptide were individually obtained using the conventional force fields,AMBER parm94, AMBER parm96, and CHARMm22. Each potential ofmean force was calibrated based on the umbrella sampling algorithm fromthe adiabatic energy map that was cal...

Reactivity of etoricoxib based on computational study of molecular orbitals, molecular electrostatic potential surface and Mulliken charge analysis

Science.gov (United States)

Sachdeva, Ritika; Soni, Abhinav; Singh, V. P.; Saini, G. S. S.

2018-05-01

Etoricoxib is one of the selective cyclooxygenase inhibitor drug which plays a significant role in the pharmacological management of arthritis and pain. The theoretical investigation of its reactivity is done using Density Functional Theory calculations. Molecular Electrostatic Potential Surface of etoricoxib and its Mulliken atomic charge distribution are used for the prediction of its electrophilic and nucleophilic sites. The detailed analysis of its frontier molecular orbitals is also done.

Transition from direct to inverted charge transport Marcus regions in molecular junctions via molecular orbital gating

Science.gov (United States)

Yuan, Li; Wang, Lejia; Garrigues, Alvar R.; Jiang, Li; Annadata, Harshini Venkata; Anguera Antonana, Marta; Barco, Enrique; Nijhuis, Christian A.

2018-04-01

Solid-state molecular tunnel junctions are often assumed to operate in the Landauer regime, which describes essentially activationless coherent tunnelling processes. In solution, on the other hand, charge transfer is described by Marcus theory, which accounts for thermally activated processes. In practice, however, thermally activated transport phenomena are frequently observed also in solid-state molecular junctions but remain poorly understood. Here, we show experimentally the transition from the Marcus to the inverted Marcus region in a solid-state molecular tunnel junction by means of intra-molecular orbital gating that can be tuned via the chemical structure of the molecule and applied bias. In the inverted Marcus region, charge transport is incoherent, yet virtually independent of temperature. Our experimental results fit well to a theoretical model that combines Landauer and Marcus theories and may have implications for the interpretation of temperature-dependent charge transport measurements in molecular junctions.

Prediction of molecular alignment of nucleic acids in aligned media

International Nuclear Information System (INIS)

Wu Bin; Petersen, Michael; Girard, Frederic; Tessari, Marco; Wijmenga, Sybren S.

2006-01-01

We demonstrate - using the data base of all deposited DNA and RNA structures aligned in Pf1-medium and RDC refined - that for nucleic acids in a Pf1-medium the electrostatic alignment tensor can be predicted reliably and accurately via a simple and fast calculation based on the gyration tensor spanned out by the phosphodiester atoms. The rhombicity is well predicted over its full range from 0 to 0.66, while the alignment tensor orientation is predicted correctly for rhombicities up to ca. 0.4, for larger rhombicities it appears to deviate somewhat more than expected based on structural noise and measurement error. This simple analytical approach is based on the Debye-Huckel approximation for the electrostatic interaction potential, valid at distances sufficiently far away from a poly-ionic charged surface, a condition naturally enforced when the charge of alignment medium and solute are of equal sign, as for nucleic acids in a Pf1-phage medium. For the usual salt strengths and nucleic acid sizes, the Debye-Huckel screening length is smaller than the nucleic acid size, but large enough for the collective of Debye-Huckel spheres to encompass the whole molecule. The molecular alignment is then purely electrostatic, but it's functional form is under these conditions similar to that for steric alignment. The proposed analytical expression allows for very fast calculation of the alignment tensor and hence RDCs from the conformation of the nucleic acid molecule. This information provides opportunities for improved structure determination of nucleic acids, including better assessment of dynamics in (multi-domain) nucleic acids and the possibility to incorporate alignment tensor prediction from shape directly into the structure calculation process. The procedures are incorporated into MATLAB scripts, which are available on request

Development of constraint algorithm for the number of electrons in molecular orbitals consisting mainly 4f atomic orbitals of rare-earth elements and its introduction to tight-binding quantum chemical molecular dynamics method

International Nuclear Information System (INIS)

Endou, Akira; Onuma, Hiroaki; Jung, Sun-ho

2007-01-01

Our original tight-binding quantum chemical molecular dynamics code, Colors', has been successfully applied to the theoretical investigation of complex materials including rare-earth elements, e.g., metal catalysts supported on a CeO 2 surface. To expand our code so as to obtain a good convergence for the electronic structure of a calculation system including a rare-earth element, we developed a novel algorithm to provide a constraint condition for the number of electrons occupying the selected molecular orbitals that mainly consist of 4f atomic orbitals of the rare-earth element. This novel algorithm was introduced in Colors. Using Colors, we succeeded in obtaining the classified electronic configurations of the 4f atomic orbitals of Ce 4+ and reduced Ce ions in a CeO 2 bulk model with one oxygen defect, which makes it difficult to obtain a good convergence using a conventional first-principles quantum chemical calculation code. (author)

Superconductivity, Mott-Hubbard states, and molecular orbital order in intercalated fullerides

CERN Document Server

Iwasa, Y

2003-01-01

This article reviews the current status of chemically doped fullerene superconductors and related compounds, with particular focus on Mott-Hubbard states and the role of molecular orbital degeneracy. Alkaline-earth metal fullerides produce superconductors of several kinds, all of which have states with higher valence than (C sub 6 sub 0) sup 6 sup - , where the second lowest unoccupied molecular orbital (the LUMO + 1 state) is filled. Alkali-metal-doped fullerides, on the other hand, afford superconductors only at the stoichiometry A sub 3 C sub 6 sub 0 (A denotes alkali metal) and in basically fcc structures. The metallicity and superconductivity of A sub 3 C sub 6 sub 0 compounds are destroyed either by reduction of the crystal symmetry or by change in the valence of C sub 6 sub 0. This difference is attributed to the narrower bandwidth in the A sub 3 C sub 6 sub 0 system, causing electronic instability in Jahn-Teller insulators and Mott-Hubbard insulators. The latter metal-insulator transition is driven by...

On the basis of molecular orbitals for relativistic bound systems of many bodies

International Nuclear Information System (INIS)

Cook, A.H.

1987-09-01

The quasi-relativistic Hamiltonian for bound states of many bodies proposed in previous articles (Cook, 1986, 1987a) is shown to provide a basis for the molecular orbital scheme of constructing wavefunctions and calculating eigenenergies. (author). 5 refs

Polaronic and dressed molecular states in orbital Feshbach resonances

Science.gov (United States)

Xu, Junjun; Qi, Ran

2018-04-01

We consider the impurity problem in an orbital Feshbach resonance (OFR), with a single excited clock state | e ↑⟩ atom immersed in a Fermi sea of electronic ground state | g ↓⟩. We calculate the polaron effective mass and quasi-particle residue, as well as the polaron to molecule transition. By including one particle-hole excitation in the molecular state, we find significant correction to the transition point. This transition point moves toward the BCS side for increasing particle densities, which suggests that the corresponding many-body physics is similar to a narrow resonance.

Spectroscopic mapping and selective electronic tuning of molecular orbitals in phosphorescent organometallic complexes – a new strategy for OLED materials

Directory of Open Access Journals (Sweden)

Pascal R. Ewen

2014-11-01

Full Text Available The improvement of molecular electronic devices such as organic light-emitting diodes requires fundamental knowledge about the structural and electronic properties of the employed molecules as well as their interactions with neighboring molecules or interfaces. We show that highly resolved scanning tunneling microscopy (STM and spectroscopy (STS are powerful tools to correlate the electronic properties of phosphorescent complexes (i.e., triplet emitters with their molecular structure as well as the local environment around a single molecule. We used spectroscopic mapping to visualize several occupied and unoccupied molecular frontier orbitals of Pt(II complexes adsorbed on Au(111. The analysis showed that the molecules exhibit a peculiar localized strong hybridization that leads to partial depopulation of a dz² orbital, while the ligand orbitals are almost unchanged. We further found that substitution of functional groups at well-defined positions can alter specific molecular orbitals without influencing the others. The results open a path toward the tailored design of electronic and optical properties of triplet emitters by smart ligand substitution, which may improve the performance of future OLED devices.

Spin orbit coupling for molecular ab initio density matrix renormalization group calculations: Application to g-tensors

Energy Technology Data Exchange (ETDEWEB)

Roemelt, Michael, E-mail: michael.roemelt@theochem.rub.de [Lehrstuhl für Theoretische Chemie, Ruhr-Universität Bochum, D-44780 Bochum, Germany and Max-Planck Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr (Germany)

2015-07-28

Spin Orbit Coupling (SOC) is introduced to molecular ab initio density matrix renormalization group (DMRG) calculations. In the presented scheme, one first approximates the electronic ground state and a number of excited states of the Born-Oppenheimer (BO) Hamiltonian with the aid of the DMRG algorithm. Owing to the spin-adaptation of the algorithm, the total spin S is a good quantum number for these states. After the non-relativistic DMRG calculation is finished, all magnetic sublevels of the calculated states are constructed explicitly, and the SOC operator is expanded in the resulting basis. To this end, spin orbit coupled energies and wavefunctions are obtained as eigenvalues and eigenfunctions of the full Hamiltonian matrix which is composed of the SOC operator matrix and the BO Hamiltonian matrix. This treatment corresponds to a quasi-degenerate perturbation theory approach and can be regarded as the molecular equivalent to atomic Russell-Saunders coupling. For the evaluation of SOC matrix elements, the full Breit-Pauli SOC Hamiltonian is approximated by the widely used spin-orbit mean field operator. This operator allows for an efficient use of the second quantized triplet replacement operators that are readily generated during the non-relativistic DMRG algorithm, together with the Wigner-Eckart theorem. With a set of spin-orbit coupled wavefunctions at hand, the molecular g-tensors are calculated following the scheme proposed by Gerloch and McMeeking. It interprets the effective molecular g-values as the slope of the energy difference between the lowest Kramers pair with respect to the strength of the applied magnetic field. Test calculations on a chemically relevant Mo complex demonstrate the capabilities of the presented method.

Investigation of the intermediate LK molecular orbital radiation in heavy ion-atom collisions

International Nuclear Information System (INIS)

Frank, W.; Kaun, K.-H.; Manfrass, P.

1981-01-01

The continuum consisting of an intensive low-energy and a high-energy components in heavy-ion atom collision systems with atomic numbers Z 1 , Z 2 > 28 is studied. The aim of the study is to prove that the C1 continuum cannot be caused by ridiative electron capture (REC) being molecular orbital (MO) radiation to the 2ptau level. It is shown that the comparison of the C1 yields obtained in Kr+Nb asymmetric collisions in gas and solid targets is associated with the formation of vacancies in the lower-Z collision partner and can be interpreted as quasimolecular radiation to the 2ptau orbital level. The strong suppression of the C2 component in the gas target experimets indicates that the MO radiation to the 1stau orbit is emitted preferentially in the two-collision process in symmetric and near-symmetric systems with Z 1 , Z 2 [ru

Localized orbitals vs. pseudopotential-plane waves basis sets: performances and accuracy for molecular magnetic systems

International Nuclear Information System (INIS)

Massobrio, C.; Ruiz, E.

2003-01-01

Density functional theory, in combination with a) a careful choice of the exchange-correlation part of the total energy and b) localized basis sets for the electronic orbital, has become the method of choice for calculating the exchange-couplings in magnetic molecular complexes. Orbital expansion on plane waves can be seen as an alternative basis set especially suited to allow optimization of newly synthesized materials of unknown geometries. However, little is known on the predictive power of this scheme to yield quantitative values for exchange coupling constants J as small as a few hundredths of eV (50-300 cm -1 ). We have used density functional theory and a plane waves basis set to calculate the exchange couplings J of three homodinuclear Cu-based molecular complexes with experimental values ranging from +40 cm -1 to -300 cm -1 . The plane waves basis set proves as accurate as the localized basis set, thereby suggesting that this approach can be reliably employed to predict and rationalize the magnetic properties of molecular-based materials. (author)

Introductory Molecular Orbital Theory: An Honors General Chemistry Computational Lab as Implemented Using Three-Dimensional Modeling Software

Science.gov (United States)

Ruddick, Kristie R.; Parrill, Abby L.; Petersen, Richard L.

2012-01-01

In this study, a computational molecular orbital theory experiment was implemented in a first-semester honors general chemistry course. Students used the GAMESS (General Atomic and Molecular Electronic Structure System) quantum mechanical software (as implemented in ChemBio3D) to optimize the geometry for various small molecules. Extended Huckel…

Modeling Photodetachment from HO2- Using the pd Case of the Generalized Mixed Character Molecular Orbital Model

Science.gov (United States)

Blackstone, Christopher C.; Sanov, Andrei

2016-06-01

Using the generalized model for photodetachment of electrons from mixed-character molecular orbitals, we gain insight into the nature of the HOMO of HO2- by treating it as a coherent superpostion of one p- and one d-type atomic orbital. Fitting the pd model function to the ab initio calculated HOMO of HO2- yields a fractional d-character, γp, of 0.979. The modeled curve of the anisotropy parameter, β, as a function of electron kinetic energy for a pd-type mixed character orbital is matched to the experimental data.

Electron-correlated fragment-molecular-orbital calculations for biomolecular and nano systems.

Science.gov (United States)

Tanaka, Shigenori; Mochizuki, Yuji; Komeiji, Yuto; Okiyama, Yoshio; Fukuzawa, Kaori

2014-06-14

Recent developments in the fragment molecular orbital (FMO) method for theoretical formulation, implementation, and application to nano and biomolecular systems are reviewed. The FMO method has enabled ab initio quantum-mechanical calculations for large molecular systems such as protein-ligand complexes at a reasonable computational cost in a parallelized way. There have been a wealth of application outcomes from the FMO method in the fields of biochemistry, medicinal chemistry and nanotechnology, in which the electron correlation effects play vital roles. With the aid of the advances in high-performance computing, the FMO method promises larger, faster, and more accurate simulations of biomolecular and related systems, including the descriptions of dynamical behaviors in solvent environments. The current status and future prospects of the FMO scheme are addressed in these contexts.

Mapping enzymatic catalysis using the effective fragment molecular orbital method

DEFF Research Database (Denmark)

Svendsen, Casper Steinmann; Fedorov, Dmitri G.; Jensen, Jan Halborg

2013-01-01

We extend the Effective Fragment Molecular Orbital (EFMO) method to the frozen domain approach where only the geometry of an active part is optimized, while the many-body polarization effects are considered for the whole system. The new approach efficiently mapped out the entire reaction path...... of chorismate mutase in less than four days using 80 cores on 20 nodes, where the whole system containing 2398 atoms is treated in the ab initio fashion without using any force fields. The reaction path is constructed automatically with the only assumption of defining the reaction coordinate a priori. We...

Molecular-orbital and structural descriptors in theoretical investigation of electroreduction of nitrodiazoles

Directory of Open Access Journals (Sweden)

BRANKO KOLARIC

2005-07-01

Full Text Available It is shown how a simple theoretical approach can be used for the investigation of electro-organic reactions.Mononitroimidazoles and mononitropyrazoles were studied by the semiempirical MNDO-PM3 molecular orbital method. The electrochemical reduction potentials of diazoles have been correlated with the energy of the lowest unoccupied molecular orbital (LUMO. It was found that an admirable correlation could be obtained by the introduction of simple structural descriptors as a correction to the energy of the LUMO. The interaction of a molecule with its surrounding depends on electrostatic potential and on steric hindrance. Most of these steric effects are taken into account using two parameters having a very limited set of integer values. The first (b is the position of a ring substituent regarding ring nitrogens, which accounts for the different orientations of dipole moments and for the different shape of the electrostatic potential. The second (structural parameter (t is the type of the ring, which accounts mostly for different modes of electrode approach, and for different charge polarization patterns in two diazole rings. The extended correlation with ELUMO, b and t, is very good, having a regression coefficient r = 0.991. The intrinsic importance of b and t is exemplified by their high statistical weight.

Molecular dynamics simulation based on the multi-component molecular orbital method: Application to H5O2+,D5O2+,andT5O2+

International Nuclear Information System (INIS)

Ishimoto, Takayoshi; Koyama, Michihisa

2012-01-01

Graphical abstract: Molecular dynamics method based on multi-component molecular orbital method was applied to basic hydrogen bonding systems, H 5 O 2 + , and its isotopomers (D 5 O 2 + andT 5 O 2 + ). Highlights: ► Molecular dynamics method with nuclear quantum effect was developed. ► Multi-component molecular orbital method was used as ab initio MO calculation. ► Developed method applied to basic hydrogen bonding system, H 5 O 2 + , and isotopomers. ► O ⋯ O vibrational stretching reflected to the distribution of protonic wavefunctions. ► H/D/T isotope effect was also analyzed. - Abstract: We propose a molecular dynamics (MD) method based on the multi-component molecular orbital (MC M O) method, which takes into account the quantum effect of proton directly, for the detailed analyses of proton transfer in hydrogen bonding system. The MC M O based MD (MC M O-MD) method is applied to the basic structures, H 5 O 2 + (called “Zundel ion”), and its isotopomers (D 5 O 2 + andT 5 O 2 + ). We clearly demonstrate the geometrical difference of hydrogen bonded O ⋯ O distance induced by H/D/T isotope effect because the O ⋯ O in H-compound was longer than that in D- or T-compound. We also find the strong relation between stretching vibration of O ⋯ O and the distribution of hydrogen bonded protonic wavefunction because the protonic wavefunction tends to delocalize when the O ⋯ O distance becomes short during the dynamics. Our proposed MC M O-MD simulation is expected as a powerful tool to analyze the proton dynamics in hydrogen bonding systems.

Chemical insight from density functional modeling of molecular adsorption: Tracking the bonding and diffusion of anthracene derivatives on Cu(111) with molecular orbitals

Science.gov (United States)

Wyrick, Jonathan; Einstein, T. L.; Bartels, Ludwig

2015-03-01

We present a method of analyzing the results of density functional modeling of molecular adsorption in terms of an analogue of molecular orbitals. This approach permits intuitive chemical insight into the adsorption process. Applied to a set of anthracene derivates (anthracene, 9,10-anthraquinone, 9,10-dithioanthracene, and 9,10-diselenonanthracene), we follow the electronic states of the molecules that are involved in the bonding process and correlate them to both the molecular adsorption geometry and the species' diffusive behavior. We additionally provide computational code to easily repeat this analysis on any system.

Kohn-Sham orbitals and potentials from quantum Monte Carlo molecular densities

International Nuclear Information System (INIS)

Varsano, Daniele; Barborini, Matteo; Guidoni, Leonardo

2014-01-01

In this work we show the possibility to extract Kohn-Sham orbitals, orbital energies, and exchange correlation potentials from accurate Quantum Monte Carlo (QMC) densities for atoms (He, Be, Ne) and molecules (H 2 , Be 2 , H 2 O, and C 2 H 4 ). The Variational Monte Carlo (VMC) densities based on accurate Jastrow Antisymmetrised Geminal Power wave functions are calculated through different estimators. Using these reference densities, we extract the Kohn-Sham quantities with the method developed by Zhao, Morrison, and Parr (ZMP) [Phys. Rev. A 50, 2138 (1994)]. We compare these extracted quantities with those obtained form CISD densities and with other data reported in the literature, finding a good agreement between VMC and other high-level quantum chemistry methods. Our results demonstrate the applicability of the ZMP procedure to QMC molecular densities, that can be used for the testing and development of improved functionals and for the implementation of embedding schemes based on QMC and Density Functional Theory

Mapping Enzymatic Catalysis Using the Effective Fragment Molecular Orbital Method: Towards all ab initio Biochemistry

DEFF Research Database (Denmark)

Svendsen, Casper Steinmann; Jensen, Jan; Fedorov, Dmitri

2013-01-01

We extend the Effective Fragment Molecular Orbital (EFMO) method to the frozen domain approach where only the geometry of an active part is optimized, while the many-body polarization effects are considered for the whole system. The new approach efficiently mapped out the entire reaction path of ...

Model Hamiltonian Calculations of the Nonlinear Polarizabilities of Conjugated Molecules.

Science.gov (United States)

Risser, Steven Michael

This dissertation advances the theoretical knowledge of the nonlinear polarizabilities of conjugated molecules. The unifying feature of these molecules is an extended delocalized pi electron structure. The pi electrons dominate the electronic properties of the molecules, allowing prediction of molecular properties based on the treatment of just the pi electrons. Two separate pi electron Hamiltonians are used in the research. The principal Hamiltonian used is the non-interacting single-particle Huckel Hamiltonian, which replaces the Coulomb interaction among the pi electrons with a mean field interaction. The simplification allows for exact solution of the Hamiltonian for large molecules. The second Hamiltonian used for this research is the interacting multi-particle Pariser-Parr-Pople (PPP) Hamiltonian, which retains explicit Coulomb interactions. This limits exact solutions to molecules containing at most eight electrons. The molecular properties being investigated are the linear polarizability, and the second and third order hyperpolarizabilities. The hyperpolarizabilities determine the nonlinear optical response of materials. These molecular parameters are determined by two independent approaches. The results from the Huckel Hamiltonian are obtained through first, second and third order perturbation theory. The results from the PPP Hamiltonian are obtained by including the applied field directly in the Hamiltonian and determining the ground state energy at a series of field strengths. By fitting the energy to a polynomial in field strength, the polarizability and hyperpolarizabilities are determined. The Huckel Hamiltonian is used to calculate the third order hyperpolarizability of polyenes. These calculations were the first to show the average hyperpolarizability of the polyenes to be positive, and also to show the saturation of the hyperpolarizability. Comparison of these Huckel results to those from the PPP Hamiltonian shows the lack of explicit Coulomb

Quantum chemical approaches: semiempirical molecular orbital and hybrid quantum mechanical/molecular mechanical techniques.

Science.gov (United States)

Bryce, Richard A; Hillier, Ian H

2014-01-01

The use of computational quantum chemical methods to aid drug discovery is surveyed. An overview of the various computational models spanning ab initio, density function theory, semiempirical molecular orbital (MO), and hybrid quantum mechanical (QM)/molecular mechanical (MM) methods is given and their strengths and weaknesses are highlighted, focussing on the challenge of obtaining the accuracy essential for them to make a meaningful contribution to drug discovery. Particular attention is given to hybrid QM/MM and semiempirical MO methods which have the potential to yield the necessary accurate predictions of macromolecular structure and reactivity. These methods are shown to have advanced the study of many aspects of substrate-ligand interactions relevant to drug discovery. Thus, the successful parametrization of semiempirical MO methods and QM/MM methods can be used to model noncovalent substrate-protein interactions, and to lead to improved scoring functions. QM/MM methods can be used in crystal structure refinement and are particularly valuable for modelling covalent protein-ligand interactions and can thus aid the design of transition state analogues. An extensive collection of examples from the areas of metalloenzyme structure, enzyme inhibition, and ligand binding affinities and scoring functions are used to illustrate the power of these techniques.

Study on the ionization of 1sσ molecular orbital in slow asymmetric collisions

International Nuclear Information System (INIS)

Sigaud, G.M.

1985-01-01

A model, based on the adiabatic perturbation theory, is proposed to the ionization of the 1sσ molecular orbital in slow asymmetric collisions. The extension of the model to less adiabatic collisions is made by imposing an asymptotic matching with the semiclassical approximation. The transient molecular state wavefunction is evaluated using an effective charge, which is dependent on the internuclear separation distance, for the projectile-target-atom-system. This procedure simulates both the screening due to the external electrons and the modifications on the electronic wavefunction due to the nuclei relative motion. The direct Coulomb ionization cross-section of the 1sσ molecular orbital is calculated for projectiles following hyperbolic paths in terms of this effective charge. At the same time, X-rays production cross-sections for the K-shell of thick targets of Ti and Fe are determined for incident beams of D, He, C, N and O, with energy range between 0,20 and 4,00 MeV. The comparison between the proposed model and the obtained experimental data shows that, for this energy range, two other processes, besides direct ionization, contribute to X-rays production. These processes, namely the recoil of the target-atom in its matrix and the electron capture by the projectile, are discussed in the light of theoretical models existent in the literature. (author)

Molecular orbitals for properties and spectroscopies

Energy Technology Data Exchange (ETDEWEB)

Robert, Vincent [Laboratoire de Chimie Quantique, Institut de Chimie, Université de Strasbourg, 1 rue Blaise Pascal 67000 Strasbourg-France (France); Domingo, Alex [Quantum Chemistry and Physical Chemistry Celestijnenlaan 200f, 3001 Heverlee - Belgium (Belgium); Braunstein, Pierre; Danopoulos, Andreas; Monakhov, Kirill [Laboratoire de Chimie de Coordination, Institut de Chimie, Université de Strasbourg, 4 rue Blaise Pascal 67081 Strasbourg-France (France)

2015-12-31

The description and clarification of spectroscopies and properties goes through ab initio calculations. Wave function based calculations (CASSCF/CASPT2) are particularly appealing since they offer spectroscopic accuracy and means of interpretation. we performed such calculations to elucidate the origin of unusual structural changes and intramolecular electron transfer phenomenon. Based on optimized molecular orbitals and a reading of the multireference wave function, it is suggested that intimate interactions are likely to considerably modify the standard pictures. A so-called PIMA (polarization-induced metalâĹŠarene) interaction similar to the more familiar anion-π interaction is responsible for a significant deviation from sp{sup 3} geometry and an energetic stabilization of 50 kJ/mol in Cr(II) benzyl organometallic complexes. In a similar fashion, it is proposed that the energetic profile of the IVCT (inter valence charge transfer) exhibits strong similarities to the Marcus’ theory, suggesting a response behaviour of the ensemble of electrons as electron transfer occurs in Fe{sup 2+}/Fe{sup 3+} bimetallic compound. The electronic reorganization induced by the IVCT process accounts for 11.8 eV, a very large effect that reduces the transfer energy down to 0.89 eV, in very good agreement with experiments.

Molecular orbital evaluation of charge flow dynamics in natural pigments based photosensitizers.

Science.gov (United States)

Heera, Thekinneydath Rajan; Cindrella, Louis

2010-03-01

The relationship between structure and photo electrochemical property of ten natural pigments from plants, insects and microbes has been analyzed using density functional theory (DFT) at the B3LYP/6-31G(d) level. The essential parameters for their photoelectrochemical behaviour such as ground state geometries, electronic transition energies and oxidation potentials are computed. The attachment tendency of the anchoring groups, expressed as the deprotonation order, is determined by calculating the proton affinities at different sites of the molecules. A thorough analysis of the charge flow dynamics in the molecular orbitals (HOMO and LUMO) of these molecules has been carried out and presented to emphasize the role of these orbitals in effective charge separation, the important feature of photosensitizers for DSSC. This study highlights that the flexible spatial orientation provided by the bridging aliphatic unsaturation favours the oscillator strength and the hydroxyl anchor group attached to the ring of delocalized pi electron cloud acts as the effective anchor.

A molecular orbital study on the oxidative decomposition of HFC-32

International Nuclear Information System (INIS)

Mochizuki, Yuji

1999-03-01

A series of ab initio molecular orbital calculations, in which Hartree-Fock, second-order Moeller-Plesset perturbation, density functional (B3LYP and BHandHLYP) levels of theory were used, was performed on the elementary reactions related to the oxidative decomposition of HFC-32 (CH 2 F 2 ) by hydroxyl (OH) radicals in a supercritical water condition (so-called SCWO). The whole process is written as CH 2 F 2 + 4OH → CO 2 + 2H 2 O + 2HF and consists of (1) H abstraction by OH to form H 2 O, (2) OH coupling to C-center, and (3) HF leaving to form C=O bond. Molecular geometries were optimized at each level of theory. The HF leaving was found to be the rate-determining step, but its barrier height was lowered by the reactive solvation with an extra H 2 O. Calculations implied that the SCWO of HFC-32 can proceed efficiently. (author)

Communication: Localized molecular orbital analysis of the effect of electron correlation on the anomalous isotope effect in the NMR spin-spin coupling constant in methane

Energy Technology Data Exchange (ETDEWEB)

Zarycz, M. Natalia C., E-mail: mnzarycz@gmail.com; Provasi, Patricio F., E-mail: patricio@unne.edu.ar [Department of Physics, University of Northeastern - CONICET, Av. Libertad 5500, Corrientes W3404AAS (Argentina); Sauer, Stephan P. A., E-mail: sauer@kiku.dk [Department of Chemistry, University of Copenhagen, Universitetsparken 5, DK-2100 Copenhagen Ø (Denmark)

2014-10-21

We discuss the effect of electron correlation on the unexpected differential sensitivity (UDS) in the {sup 1}J(C–H) coupling constant of CH{sub 4} using a decomposition into contributions from localized molecular orbitals and compare with the {sup 1}J(N–H) coupling constant in NH{sub 3}. In particular, we discuss the well known fact that uncorrelated coupled Hartree-Fock (CHF) calculations are not able to reproduce the UDS in methane. For this purpose we have implemented for the first time a localized molecular orbital analysis for the second order polarization propagator approximation with coupled cluster singles and doubles amplitudes—SOPPA(CCSD) in the DALTON program. Comparing the changes in the localized orbital contributions at the correlated SOPPA and SOPPA(CCSD) levels and at the uncorrelated CHF level, we find that the latter overestimates the effect of stretching the bond between the coupled atoms on the contribution to the coupling from the localized bonding orbital between these atoms. This disturbs the subtle balance between the molecular orbital contributions, which lead to the UDS in methane.

Fragment-orbital tunneling currents and electronic couplings for analysis of molecular charge-transfer systems.

Science.gov (United States)

Hwang, Sang-Yeon; Kim, Jaewook; Kim, Woo Youn

2018-04-04

In theoretical charge-transfer research, calculation of the electronic coupling element is crucial for examining the degree of the electronic donor-acceptor interaction. The tunneling current (TC), representing the magnitudes and directions of electron flow, provides a way of evaluating electronic couplings, along with the ability of visualizing how electrons flow in systems. Here, we applied the TC theory to π-conjugated organic dimer systems, in the form of our fragment-orbital tunneling current (FOTC) method, which uses the frontier molecular-orbitals of system fragments as diabatic states. For a comprehensive test of FOTC, we assessed how reasonable the computed electronic couplings and the corresponding TC densities are for the hole- and electron-transfer databases HAB11 and HAB7. FOTC gave 12.5% mean relative unsigned error with regard to the high-level ab initio reference. The shown performance is comparable with that of fragment-orbital density functional theory, which gave the same error by 20.6% or 13.9% depending on the formulation. In the test of a set of nucleobase π stacks, we showed that the original TC expression is also applicable to nondegenerate cases under the condition that the overlap between the charge distributions of diabatic states is small enough to offset the energy difference. Lastly, we carried out visual analysis on the FOTC densities of thiophene dimers with different intermolecular alignments. The result depicts an intimate topological connection between the system geometry and electron flow. Our work provides quantitative and qualitative grounds for FOTC, showing it to be a versatile tool in characterization of molecular charge-transfer systems.

Quantum analysis in the transition process to excited state of an oxygen molecule induced by electron collisions; Denshi shototsu ni tomonau sanso bunshi ni okeru reiki jotai sen`i no ryoshironteki kaiseki

Energy Technology Data Exchange (ETDEWEB)

Ishimaru, K. [Gifu National College of Technology, Gifu (Japan); Okazaki, K. [Tokyo Inst. of Technology, Tokyo (Japan)

1996-06-25

For understanding of fundamental chemical reactions under a highly non equilibrium condition which is quite often used in plasma processing, the relevant atomic and molecular processes must be clarified. In this study, an analysis of the transition process to the excited state of an oxygen molecule induced by electron collisions in the oxygen plasma has been carried out. First, the electron density distribution in an oxygen molecule has been calculated using the extended Huckel molecular orbital method. Then, the electron potential energy distribution in the transition process to the excited state has been estimated. The electron behavior has been calculated using the estimated unidimensional electron potential energy distribution and unsteady quantum mechanics. As a result, the transition process to the excited state of an oxygen molecule induced by electron collisions and its conditions have been clarified qualitatively. 9 refs., 9 figs.

Localized orbitals vs. pseudopotential-plane waves basis sets: performances and accuracy for molecular magnetic systems

CERN Document Server

Massobrio, C

2003-01-01

Density functional theory, in combination with a) a careful choice of the exchange-correlation part of the total energy and b) localized basis sets for the electronic orbital, has become the method of choice for calculating the exchange-couplings in magnetic molecular complexes. Orbital expansion on plane waves can be seen as an alternative basis set especially suited to allow optimization of newly synthesized materials of unknown geometries. However, little is known on the predictive power of this scheme to yield quantitative values for exchange coupling constants J as small as a few hundredths of eV (50-300 cm sup - sup 1). We have used density functional theory and a plane waves basis set to calculate the exchange couplings J of three homodinuclear Cu-based molecular complexes with experimental values ranging from +40 cm sup - sup 1 to -300 cm sup - sup 1. The plane waves basis set proves as accurate as the localized basis set, thereby suggesting that this approach can be reliably employed to predict and r...

Molecular Electronic Terms and Molecular Orbital Configurations.

Science.gov (United States)

Mazo, R. M.

1990-01-01

Discussed are the molecular electronic terms which can arise from a given electronic configuration. Considered are simple cases, molecular states, direct products, closed shells, and open shells. Two examples are provided. (CW)

Systematic determination of extended atomic orbital basis sets and application to molecular SCF and MCSCF calculations

Energy Technology Data Exchange (ETDEWEB)

Feller, D.F.

1979-01-01

The behavior of the two exponential parameters in an even-tempered gaussian basis set is investigated as the set optimally approaches an integral transform representation of the radial portion of atomic and molecular orbitals. This approach permits a highly accurate assessment of the Hartree-Fock limit for atoms and molecules.

Molecular orbital study of iron pentacarbonyl and its photochemical fragments Fe(CO) sub(n)

International Nuclear Information System (INIS)

Guenzburger, D.J.R.; Saitovitch, E.M.B.; De Paoli, M.-A.; Manella, H.

1982-01-01

Self-consistent Molecular Orbital calculations were performed for Fe(CO) 5 and its photofragments Fe(CO) sub(n), 1 5 , photoelectron and optical spectra are analysed, and photochemical behaviour is discussed. The Moessbauer isomer shifts and quadrupole splittings are investigated. In the case of Fe(CO) 5 and Fe(CO) 4 , the values derived for these hyperfine interactions are compared to experimental measurements reported in a polyethylene matrix. (Author) [pt

Performance assessment of semiempirical molecular orbital methods in describing halogen bonding: quantum mechanical and quantum mechanical/molecular mechanical-molecular dynamics study.

Science.gov (United States)

Ibrahim, Mahmoud A A

2011-10-24

The performance of semiempirical molecular-orbital methods--MNDO, MNDO-d, AM1, RM1, PM3 and PM6--in describing halogen bonding was evaluated, and the results were compared with molecular mechanical (MM) and quantum mechanical (QM) data. Three types of performance were assessed: (1) geometrical optimizations and binding energy calculations for 27 halogen-containing molecules complexed with various Lewis bases (Two of the tested methods, AM1 and RM1, gave results that agree with the QM data.); (2) charge distribution calculations for halobenzene molecules, determined by calculating the solvation free energies of the molecules relative to benzene in explicit and implicit generalized Born (GB) solvents (None of the methods gave results that agree with the experimental data.); and (3) appropriateness of the semiempirical methods in the hybrid quantum-mechanical/molecular-mechanical (QM/MM) scheme, investigated by studying the molecular inhibition of CK2 protein by eight halobenzimidazole and -benzotriazole derivatives using hybrid QM/MM molecular-dynamics (MD) simulations with the inhibitor described at the QM level by the AM1 method and the rest of the system described at the MM level. The pure MM approach with inclusion of an extra point of positive charge on the halogen atom approach gave better results than the hybrid QM/MM approach involving the AM1 method. Also, in comparison with the pure MM-GBSA (generalized Born surface area) binding energies and experimental data, the calculated QM/MM-GBSA binding energies of the inhibitors were improved by replacing the G(GB,QM/MM) solvation term with the corresponding G(GB,MM) term.

Study of high-performance canonical molecular orbitals calculation for proteins

Science.gov (United States)

Hirano, Toshiyuki; Sato, Fumitoshi

2017-11-01

The canonical molecular orbital (CMO) calculation can help to understand chemical properties and reactions in proteins. However, it is difficult to perform the CMO calculation of proteins because of its self-consistent field (SCF) convergence problem and expensive computational cost. To certainly obtain the CMO of proteins, we work in research and development of high-performance CMO applications and perform experimental studies. We have proposed the third-generation density-functional calculation method of calculating the SCF, which is more advanced than the FILE and direct method. Our method is based on Cholesky decomposition for two-electron integrals calculation and the modified grid-free method for the pure-XC term evaluation. By using the third-generation density-functional calculation method, the Coulomb, the Fock-exchange, and the pure-XC terms can be given by simple linear algebraic procedure in the SCF loop. Therefore, we can expect to get a good parallel performance in solving the SCF problem by using a well-optimized linear algebra library such as BLAS on the distributed memory parallel computers. The third-generation density-functional calculation method is implemented to our program, ProteinDF. To achieve computing electronic structure of the large molecule, not only overcoming expensive computation cost and also good initial guess for safe SCF convergence are required. In order to prepare a precise initial guess for the macromolecular system, we have developed the quasi-canonical localized orbital (QCLO) method. The QCLO has the characteristics of both localized and canonical orbital in a certain region of the molecule. We have succeeded in the CMO calculations of proteins by using the QCLO method. For simplified and semi-automated calculation of the QCLO method, we have also developed a Python-based program, QCLObot.

Simulation of charge transfer and orbital rehybridization in molecular and condensed matter systems

Science.gov (United States)

Nistor, Razvan A.

The mixing and shifting of electronic orbitals in molecules, or between atoms in bulk systems, is crucially important to the overall structure and physical properties of materials. Understanding and accurately modeling these orbital interactions is of both scientific and industrial relevance. Electronic orbitals can be perturbed in several ways. Doping, adding or removing electrons from systems, can change the bond-order and the physical properties of certain materials. Orbital rehybridization, driven by either thermal or pressure excitation, alters the short-range structure of materials and changes their long-range transport properties. Macroscopically, during bond formation, the shifting of electronic orbitals can be interpreted as a charge transfer phenomenon, as electron density may pile up around, and hence, alter the effective charge of, a given atom in the changing chemical environment. Several levels of theory exist to elucidate the mechanisms behind these orbital interactions. Electronic structure calculations solve the time-independent Schrodinger equation to high chemical accuracy, but are computationally expensive and limited to small system sizes and simulation times. Less fundamental atomistic calculations use simpler parameterized functional expressions called force-fields to model atomic interactions. Atomistic simulations can describe systems and time-scales larger and longer than electronic-structure methods, but at the cost of chemical accuracy. In this thesis, both first-principles and phenomenological methods are addressed in the study of several encompassing problems dealing with charge transfer and orbital rehybridization. Firstly, a new charge-equilibration method is developed that improves upon existing models to allow next-generation force-fields to describe the electrostatics of changing chemical environments. Secondly, electronic structure calculations are used to investigate the doping dependent energy landscapes of several high

Molecular docking, TG/DTA, molecular structure, harmonic vibrational frequencies, natural bond orbital and TD-DFT analysis of diphenyl carbonate by DFT approach

Science.gov (United States)

Xavier, S.; Periandy, S.; Carthigayan, K.; Sebastian, S.

2016-12-01

Vibrational spectral analysis of Diphenyl Carbonate (DPC) is carried out by using FT-IR and FT-Raman spectroscopic techniques. It is found that all vibrational modes are in the expected region. Gaussian computational calculations were performed using B3LYP method with 6-311++G (d, p) basis set. The computed geometric parameters are in good agreement with XRD data. The observation shows that the structure of the carbonate group is unsymmetrical by ∼5° due to the attachment of the two phenyl rings. The stability of the molecule arising from hyperconjugative interaction and charge delocalization are analyzed by Natural Bond Orbital (NBO) study and the results show the lone pair transition has higher stabilization energy compared to all other. The 1H and 13C NMR chemical shifts are calculated using the Gauge-Including Atomic Orbital (GIAO) method with B3LYP/6-311++G (d, p) method. The chemical shifts computed theoretically go very closer to the experimental results. A study on the electronic and optical properties; absorption wavelengths, excitation energy, dipole moment and frontier molecular orbital energies and Molecular electrostatic potential (MEP) exhibit the high reactivity nature of the molecule. The non-linear optical property of the DPC molecule predicted theoretically found to be good candidate for NLO material. TG/DTA analysis was made and decomposition of the molecule with respect to the temperature was studied. DPC having the anthelmintic activity is docked in the Hemoglobin of Fasciola hepatica protein. The DPC has been screened to antimicrobial activity and found to exhibit antibacterial effects.

Prediction of complexes of uranyl and organic substances by molecular orbital calculation

International Nuclear Information System (INIS)

Nagasaki, S.; Tsushima, S.; Todoriki, M.; Tanaka, S.; Suzuki, A.

1999-01-01

Structure of UO 2 2+ complexes with salicylic acid was optimized by using molecular orbital calculation (ab initio method). The bond distances between U and O atoms (O eq ) of carboxyl group and phenyl group in salicylic acid were evaluated and compared with those measured experimentally by Denecke et al. The calculated distance relatively agrees with the experimental one. The frontier electron densities in the complexes were also calculated. Strong localization of frontier electron density in the complexes was not observed, suggesting that the complexes are subject to only weak interactions with rocks, minerals and other compounds in the geosphere. (author)

Matrix isolation FT-IR spectroscopy and molecular orbital study of sarcosine methyl ester

OpenAIRE

Gómez-Zavaglia, Andrea; Fausto, R.

2004-01-01

N-methylglycine methyl ester (sarcosine-Me) has been studied by matrix isolation FT-IR spectroscopy and molecular orbital calculations undertaken at the DFT/B3LYP and MP2 levels of theory with the 6-311++G(d,p) and 6-31++G(d,p) basis set, respectively. Twelve different conformers were located in the potential energy surface of the studied compound, with the ASC conformer being the ground conformational state. This form is analogous to the dimethylglycine methyl ester most stable conformer and...

Enhanced Magnetoresistance in Molecular Junctions by Geometrical Optimization of Spin-Selective Orbital Hybridization.

Science.gov (United States)

Rakhmilevitch, David; Sarkar, Soumyajit; Bitton, Ora; Kronik, Leeor; Tal, Oren

2016-03-09

Molecular junctions based on ferromagnetic electrodes allow the study of electronic spin transport near the limit of spintronics miniaturization. However, these junctions reveal moderate magnetoresistance that is sensitive to the orbital structure at their ferromagnet-molecule interfaces. The key structural parameters that should be controlled in order to gain high magnetoresistance have not been established, despite their importance for efficient manipulation of spin transport at the nanoscale. Here, we show that single-molecule junctions based on nickel electrodes and benzene molecules can yield a significant anisotropic magnetoresistance of up to ∼200% near the conductance quantum G0. The measured magnetoresistance is mechanically tuned by changing the distance between the electrodes, revealing a nonmonotonic response to junction elongation. These findings are ascribed with the aid of first-principles calculations to variations in the metal-molecule orientation that can be adjusted to obtain highly spin-selective orbital hybridization. Our results demonstrate the important role of geometrical considerations in determining the spin transport properties of metal-molecule interfaces.

A hybrid framework of first principles molecular orbital calculations and a three-dimensional integral equation theory for molecular liquids: Multi-center molecular Ornstein-Zernike self-consistent field approach

Science.gov (United States)

Kido, Kentaro; Kasahara, Kento; Yokogawa, Daisuke; Sato, Hirofumi

2015-07-01

In this study, we reported the development of a new quantum mechanics/molecular mechanics (QM/MM)-type framework to describe chemical processes in solution by combining standard molecular-orbital calculations with a three-dimensional formalism of integral equation theory for molecular liquids (multi-center molecular Ornstein-Zernike (MC-MOZ) method). The theoretical procedure is very similar to the 3D-reference interaction site model self-consistent field (RISM-SCF) approach. Since the MC-MOZ method is highly parallelized for computation, the present approach has the potential to be one of the most efficient procedures to treat chemical processes in solution. Benchmark tests to check the validity of this approach were performed for two solute (solute water and formaldehyde) systems and a simple SN2 reaction (Cl- + CH3Cl → ClCH3 + Cl-) in aqueous solution. The results for solute molecular properties and solvation structures obtained by the present approach were in reasonable agreement with those obtained by other hybrid frameworks and experiments. In particular, the results of the proposed approach are in excellent agreements with those of 3D-RISM-SCF.

A hybrid framework of first principles molecular orbital calculations and a three-dimensional integral equation theory for molecular liquids: multi-center molecular Ornstein-Zernike self-consistent field approach.

Science.gov (United States)

Kido, Kentaro; Kasahara, Kento; Yokogawa, Daisuke; Sato, Hirofumi

2015-07-07

In this study, we reported the development of a new quantum mechanics/molecular mechanics (QM/MM)-type framework to describe chemical processes in solution by combining standard molecular-orbital calculations with a three-dimensional formalism of integral equation theory for molecular liquids (multi-center molecular Ornstein-Zernike (MC-MOZ) method). The theoretical procedure is very similar to the 3D-reference interaction site model self-consistent field (RISM-SCF) approach. Since the MC-MOZ method is highly parallelized for computation, the present approach has the potential to be one of the most efficient procedures to treat chemical processes in solution. Benchmark tests to check the validity of this approach were performed for two solute (solute water and formaldehyde) systems and a simple SN2 reaction (Cl(-) + CH3Cl → ClCH3 + Cl(-)) in aqueous solution. The results for solute molecular properties and solvation structures obtained by the present approach were in reasonable agreement with those obtained by other hybrid frameworks and experiments. In particular, the results of the proposed approach are in excellent agreements with those of 3D-RISM-SCF.

Energy Decomposition Analysis Based on Absolutely Localized Molecular Orbitals for Large-Scale Density Functional Theory Calculations in Drug Design.

Science.gov (United States)

Phipps, M J S; Fox, T; Tautermann, C S; Skylaris, C-K

2016-07-12

We report the development and implementation of an energy decomposition analysis (EDA) scheme in the ONETEP linear-scaling electronic structure package. Our approach is hybrid as it combines the localized molecular orbital EDA (Su, P.; Li, H. J. Chem. Phys., 2009, 131, 014102) and the absolutely localized molecular orbital EDA (Khaliullin, R. Z.; et al. J. Phys. Chem. A, 2007, 111, 8753-8765) to partition the intermolecular interaction energy into chemically distinct components (electrostatic, exchange, correlation, Pauli repulsion, polarization, and charge transfer). Limitations shared in EDA approaches such as the issue of basis set dependence in polarization and charge transfer are discussed, and a remedy to this problem is proposed that exploits the strictly localized property of the ONETEP orbitals. Our method is validated on a range of complexes with interactions relevant to drug design. We demonstrate the capabilities for large-scale calculations with our approach on complexes of thrombin with an inhibitor comprised of up to 4975 atoms. Given the capability of ONETEP for large-scale calculations, such as on entire proteins, we expect that our EDA scheme can be applied in a large range of biomolecular problems, especially in the context of drug design.

X-ray Constrained Extremely Localized Molecular Orbitals: Theory and Critical Assessment of the New Technique.

Science.gov (United States)

Genoni, Alessandro

2013-07-09

Following the X-ray constrained wave function approach proposed by Jayatilaka, we have devised a new technique that allows to extract molecular orbitals strictly localized on small molecular fragments from sets of experimental X-ray structure factors amplitudes. Since the novel strategy enables to obtain electron distributions that have quantum mechanical features and that can be easily interpreted in terms of traditional chemical concepts, the method can be also considered as a new useful tool for the determination and the analysis of charge densities from high-resolution X-ray experiments. In this paper, we describe in detail the theory of the new technique, which, in comparison to our preliminary work, has been improved both treating the effects of isotropic secondary extinctions and introducing a new protocol to halt the fitting procedure against the experimental X-ray scattering data. The performances of the novel strategy have been studied both in function of the basis-sets flexibility and in function of the quality of the considered crystallographic data. The tests performed on four different systems (α-glycine, l-cysteine, (aminomethyl)phosphonic acid and N-(trifluoromethyl)formamide) have shown that the achievement of good statistical agreements with the experimental measures mainly depends on the quality of the crystal structures (i.e., geometry positions and thermal parameters) used in the X-ray constrained calculations. Finally, given the reliable transferability of the obtained Extremely Localized Molecular Orbitals (ELMOs), we envisage to exploit the novel approach to construct new ELMOs databases suited to the development of linear-scaling methods for the refinement of macromolecular crystal structures.

A hybrid framework of first principles molecular orbital calculations and a three-dimensional integral equation theory for molecular liquids: Multi-center molecular Ornstein–Zernike self-consistent field approach

International Nuclear Information System (INIS)

Kido, Kentaro; Kasahara, Kento; Yokogawa, Daisuke; Sato, Hirofumi

2015-01-01

In this study, we reported the development of a new quantum mechanics/molecular mechanics (QM/MM)-type framework to describe chemical processes in solution by combining standard molecular-orbital calculations with a three-dimensional formalism of integral equation theory for molecular liquids (multi-center molecular Ornstein–Zernike (MC-MOZ) method). The theoretical procedure is very similar to the 3D-reference interaction site model self-consistent field (RISM-SCF) approach. Since the MC-MOZ method is highly parallelized for computation, the present approach has the potential to be one of the most efficient procedures to treat chemical processes in solution. Benchmark tests to check the validity of this approach were performed for two solute (solute water and formaldehyde) systems and a simple S N 2 reaction (Cl − + CH 3 Cl → ClCH 3 + Cl − ) in aqueous solution. The results for solute molecular properties and solvation structures obtained by the present approach were in reasonable agreement with those obtained by other hybrid frameworks and experiments. In particular, the results of the proposed approach are in excellent agreements with those of 3D-RISM-SCF

Application of TensorFlow to recognition of visualized results of fragment molecular orbital (FMO) calculations

OpenAIRE

Saitou, Sona; Iijima, Jun; Fujimoto, Mayu; Mochizuki, Yuji; Okuwaki, Koji; Doi, Hideo; Komeiji, Yuto

2018-01-01

We have applied Google's TensorFlow deep learning toolkit to recognize the visualized results of the fragment molecular orbital (FMO) calculations. Typical protein structures of alpha-helix and beta-sheet provide some characteristic patterns in the two-dimensional map of inter-fragment interaction energy termed as IFIE-map (Kurisaki et al., Biophys. Chem. 130 (2007) 1). A thousand of IFIE-map images with labels depending on the existences of alpha-helix and beta-sheet were prepared by employi...

Ab initio effective core potentials for molecular calculations. Potentials for K to Au including the outermost core orbitals

International Nuclear Information System (INIS)

Hay, P.J.; Wadt, W.R.

1985-01-01

Ab initio effective core potentials (ECP's) have been generated to replace the innermost core electron for third-row (K--Au), fourth-row (Rb--Ag), and fifth-row (Cs--Au) atoms. The outermost core orbitals: corresponding to the ns 2 np 6 configuration for the three rows here: are not replaced by the ECP but are treated on an equal footing with the nd, (n+1)s and (n+1)p valence orbitals. These ECP's have been derived for use in molecular calculations where these outer core orbitals need to be treated explicitly rather than to be replaced by an ECP. The ECP's for the forth and fifth rows also incorporate the mass--velocity and Darwin relativistic effects into the potentials. Analytic fits to the potentials are presented for use in multicenter integral evaluation. Gaussian orbital valence basis sets are developed for the (3s, 3p, 3d, 4s, 4p), (4s, 4p, 4d, 5s, 5p), and (5s, 5p, 5d, 6s, 6p) ortibals of the three respective rows

Effective screening length and quasiuniversality for the restricted primitive model of an electrolyte solution.

Science.gov (United States)

Janecek, Jirí; Netz, Roland R

2009-02-21

Monte Carlo simulations for the restricted primitive model of an electrolyte solution above the critical temperature are performed at a wide range of concentrations and temperatures. Thermodynamic properties such as internal energy, osmotic coefficient, activity coefficient, as well as spatial correlation functions are determined. These observables are used to investigate whether quasiuniversality in terms of an effective screening length exists, similar to the role played by the effective electron mass in solid-state physics. To that end, an effective screening length is extracted from the asymptotic behavior of the Fourier-transformed charge-correlation function and plugged into the Debye-Huckel limiting expressions for various thermodynamic properties. Comparison with numerical results is favorable, suggesting that correlation and other effects not captured on the Debye-Huckel limiting level can be successfully incorporated by a single effective parameter while keeping the functional form of Debye-Huckel expressions. We also compare different methods to determine mean ionic activity coefficient in molecular simulations and check the internal consistency of the numerical data.

Construction of the Fock Matrix on a Grid-Based Molecular Orbital Basis Using GPGPUs.

Science.gov (United States)

Losilla, Sergio A; Watson, Mark A; Aspuru-Guzik, Alán; Sundholm, Dage

2015-05-12

We present a GPGPU implementation of the construction of the Fock matrix in the molecular orbital basis using the fully numerical, grid-based bubbles representation. For a test set of molecules containing up to 90 electrons, the total Hartree-Fock energies obtained from reference GTO-based calculations are reproduced within 10(-4) Eh to 10(-8) Eh for most of the molecules studied. Despite the very large number of arithmetic operations involved, the high performance obtained made the calculations possible on a single Nvidia Tesla K40 GPGPU card.

Introduction to Computational Chemistry: Teaching Hu¨ckel Molecular Orbital Theory Using an Excel Workbook for Matrix Diagonalization

Science.gov (United States)

Litofsky, Joshua; Viswanathan, Rama

2015-01-01

Matrix diagonalization, the key technique at the heart of modern computational chemistry for the numerical solution of the Schrödinger equation, can be easily introduced in the physical chemistry curriculum in a pedagogical context using simple Hückel molecular orbital theory for p bonding in molecules. We present details and results of…

The effect of electrodes on 11 acene molecular spin valve: Semi-empirical study

Science.gov (United States)

Aadhityan, A.; Preferencial Kala, C.; John Thiruvadigal, D.

2017-10-01

A new revolution in electronics is molecular spintronics, with the contemporary evolution of the two novel disciplines of spintronics and molecular electronics. The key point is the creation of molecular spin valve which consists of a diamagnetic molecule in between two magnetic leads. In this paper, non-equilibrium Green's function (NEGF) combined with Extended Huckel Theory (EHT); a semi-empirical approach is used to analyse the electron transport characteristics of 11 acene molecular spin valve. We examine the spin-dependence transport on 11 acene molecular junction with various semi-infinite electrodes as Iron, Cobalt and Nickel. To analyse the spin-dependence transport properties the left and right electrodes are joined to the central region in parallel and anti-parallel configurations. We computed spin polarised device density of states, projected device density of states of carbon and the electrode element, and transmission of these devices. The results demonstrate that the effect of electrodes modifying the spin-dependence behaviours of these systems in a controlled way. In Parallel and anti-parallel configuration the separation of spin up and spin down is lager in the case of iron electrode than nickel and cobalt electrodes. It shows that iron is the best electrode for 11 acene spin valve device. Our theoretical results are reasonably impressive and trigger our motivation for comprehending the transport properties of these molecular-sized contacts.

The effective fragment molecular orbital method for fragments connected by covalent bonds.

Directory of Open Access Journals (Sweden)

Casper Steinmann

Full Text Available We extend the effective fragment molecular orbital method (EFMO into treating fragments connected by covalent bonds. The accuracy of EFMO is compared to FMO and conventional ab initio electronic structure methods for polypeptides including proteins. Errors in energy for RHF and MP2 are within 2 kcal/mol for neutral polypeptides and 6 kcal/mol for charged polypeptides similar to FMO but obtained two to five times faster. For proteins, the errors are also within a few kcal/mol of the FMO results. We developed both the RHF and MP2 gradient for EFMO. Compared to ab initio, the EFMO optimized structures had an RMSD of 0.40 and 0.44 Å for RHF and MP2, respectively.

A semi-empirical molecular orbital model of silica, application to radiation compaction

International Nuclear Information System (INIS)

Tasker, P.W.

1978-11-01

Semi-empirical molecular-orbital theory is used to calculate the bonding in a cluster of two SiO 4 tetrahedra, with the outer bonds saturated with pseudo-hydrogen atoms. The basic properties of the cluster, bond energies and band gap are calculated using a very simple parameterisation scheme. The resulting cluster is used to study the rebonding that occurs when an oxygen vacancy is created. It is suggested that a vacancy model is capable of producing the observed differences between quartz and vitreous silica, and the calculations show that the compaction effect observed in the glass is of a magnitude compatible with the relaxations around the vacancy. More detailed lattice models will be needed to examine this mechanism further. (author)

Pinning of fullerene lowest unoccupied molecular orbital edge at the interface with standing up copper phthalocyanine

International Nuclear Information System (INIS)

Wang, Chenggong; Irfan, Irfan; Turinske, Alexander J.; Gao, Yongli

2012-01-01

The electronic structure evolution of interfaces of fullerene (C 60 ) with copper phthalocyanine (CuPc) on highly oriented pyrolitic graphite (HOPG) and on native silicon oxide has been investigated with ultra-violet photoemission spectroscopy and inverse photoemission spectroscopy. The lowest unoccupied molecular orbital edge of C 60 was found to be pinned at the interface with CuPc on SiO 2 . A substantial difference in the electron affinity of CuPc on the two substrates was observed as the orientation of CuPc is lying flat on HOPG and standing up on SiO 2 . The ionization potential and electron affinity of C 60 were not affected by the orientation of CuPc due to the spherical symmetry of C 60 molecules. We observed band bending in C 60 on the standing-up orientation of CuPc molecules, while the energy levels of C 60 on the flat lying orientation of CuPc molecules were observed to be flat. - Highlights: ► Orientation of copper phthalocyanine (CuPc) on ordered graphite and silicon oxide. ► Pinning of lowest unoccupied molecular orbital edge of C60 to the Fermi level on CuPc. ► No C60 pinning or band bending was observed on flat laying CuPc. ► Results are useful for organic photovoltaic and organic light emitting diode research.

Restricted active space calculations of L-edge X-ray absorption spectra: from molecular orbitals to multiplet states.

Science.gov (United States)

Pinjari, Rahul V; Delcey, Mickaël G; Guo, Meiyuan; Odelius, Michael; Lundberg, Marcus

2014-09-28

The metal L-edge (2p → 3d) X-ray absorption spectra are affected by a number of different interactions: electron-electron repulsion, spin-orbit coupling, and charge transfer between metal and ligands, which makes the simulation of spectra challenging. The core restricted active space (RAS) method is an accurate and flexible approach that can be used to calculate X-ray spectra of a wide range of medium-sized systems without any symmetry constraints. Here, the applicability of the method is tested in detail by simulating three ferric (3d(5)) model systems with well-known electronic structure, viz., atomic Fe(3+), high-spin [FeCl6](3-) with ligand donor bonding, and low-spin [Fe(CN)6](3-) that also has metal backbonding. For these systems, the performance of the core RAS method, which does not require any system-dependent parameters, is comparable to that of the commonly used semi-empirical charge-transfer multiplet model. It handles orbitally degenerate ground states, accurately describes metal-ligand interactions, and includes both single and multiple excitations. The results are sensitive to the choice of orbitals in the active space and this sensitivity can be used to assign spectral features. A method has also been developed to analyze the calculated X-ray spectra using a chemically intuitive molecular orbital picture.

A third-generation density-functional-theory-based method for calculating canonical molecular orbitals of large molecules.

Science.gov (United States)

Hirano, Toshiyuki; Sato, Fumitoshi

2014-07-28

We used grid-free modified Cholesky decomposition (CD) to develop a density-functional-theory (DFT)-based method for calculating the canonical molecular orbitals (CMOs) of large molecules. Our method can be used to calculate standard CMOs, analytically compute exchange-correlation terms, and maximise the capacity of next-generation supercomputers. Cholesky vectors were first analytically downscaled using low-rank pivoted CD and CD with adaptive metric (CDAM). The obtained Cholesky vectors were distributed and stored on each computer node in a parallel computer, and the Coulomb, Fock exchange, and pure exchange-correlation terms were calculated by multiplying the Cholesky vectors without evaluating molecular integrals in self-consistent field iterations. Our method enables DFT and massively distributed memory parallel computers to be used in order to very efficiently calculate the CMOs of large molecules.

Spin-orbital superexchange physics emerging from interacting oxygen molecules in KO2

International Nuclear Information System (INIS)

Solovyev, I V

2008-01-01

We propose that the spin-orbital-lattice coupled phenomena, widely known for the transition-metal oxides, can be realized in molecular solids, comprising of orbitally degenerate magnetic O 2 - ions. KO 2 is one such system. Using the first-principles electronic structure calculations, we set-up an effective spin-orbital superexchange model for the low-energy molecular bands and argue that many anomalous properties of KO 2 indeed replicate the status of its orbital system in different temperature regimes

Conformational study of sarcosine as probed by matrix-isolation FT-IR spectroscopy and molecular orbital calculations

OpenAIRE

Gómez-Zavaglia, Andrea; Fausto, R.

2003-01-01

Sarcosine (N-methylglycine) has been studied by matrix-isolation FT-IR spectroscopy and molecular orbital calculations undertaken at the DFT/B3LYP and MP2 levels of theory with the 6-311++G(d, p) and 6-31++G(d, p) basis set, respectively. Eleven different conformers were located in the potential energy surface (PES) of sarcosine, with the ASC conformer being the ground conformational state. This form is analogous to the glycine most stable conformer and is characterized by a NH...O= intramole...

MgH Rydberg series: Transition energies from electron propagator theory and oscillator strengths from the molecular quantum defect orbital method

Science.gov (United States)

Corzo, H. H.; Velasco, A. M.; Lavín, C.; Ortiz, J. V.

2018-02-01

Vertical excitation energies belonging to several Rydberg series of MgH have been inferred from 3+ electron-propagator calculations of the electron affinities of MgH+ and are in close agreement with experiment. Many electronically excited states with n > 3 are reported for the first time and new insight is given on the assignment of several Rydberg series. Valence and Rydberg excited states of MgH are distinguished respectively by high and low pole strengths corresponding to Dyson orbitals of electron attachment to the cation. By applying the Molecular Quantum Defect Orbital method, oscillator strengths for electronic transitions involving Rydberg states also have been determined.

a Moessbauer Effect and Fenske-Hall Molecular Orbital Study of the Electronic Properties of Organoiron Clusters.

Science.gov (United States)

Buhl, Margaret Linn

The electronic properties of trinuclear iron, tetranuclear iron butterfly, iron-cobalt, and iron-copper clusters have been studied experimentally at 78K by the Mossbauer effect and theoretically by Fenske-Hall molecular orbital calculations. The Mossbauer effect isomer shift is very sensitive to the differences in the iron s-electron densities in these clusters and, as expected, decreases as the sum of the iron 4s Mulliken population and the Clementi and Raimondi effective nuclear charge increases. The molecular orbital wave functions and the Mulliken atomic charges are used to calculate the electric field gradient at the metal nuclei and the iron Mossbauer effect quadrupole splittings. The valence contribution was found to be the major component of the electric field gradient in all the clusters studied. In general the calculated value of Delta E_ {Q} is larger than the observed value, as a result of neglect of the valence Sternheimer factor, R. The metal charge depends upon its electronegativity and upon the nature of its Lewis base ligands. The carbonyl ligand carbon charge becomes more positive as the metal electronegativity increases. The oxygen charge becomes more negative as the anionic cluster charge increases, and in so doing, yields the maximum anionic charge separation. The electronic properties of the terminal carbonyl ligands are similar to those of carbon monoxide, whereas the electronic properties of the bridging carbonyl ligands are similar to those of the carbonyl group found in aldehydes and ketones.

A Modified ELISA Accurately Measures Secretion of High Molecular Weight Hyaluronan (HA) by Graves' Disease Orbital Cells

Science.gov (United States)

Krieger, Christine C.

2014-01-01

Excess production of hyaluronan (hyaluronic acid [HA]) in the retro-orbital space is a major component of Graves' ophthalmopathy, and regulation of HA production by orbital cells is a major research area. In most previous studies, HA was measured by ELISAs that used HA-binding proteins for detection and rooster comb HA as standards. We show that the binding efficiency of HA-binding protein in the ELISA is a function of HA polymer size. Using gel electrophoresis, we show that HA secreted from orbital cells is primarily comprised of polymers more than 500 000. We modified a commercially available ELISA by using 1 million molecular weight HA as standard to accurately measure HA of this size. We demonstrated that IL-1β-stimulated HA secretion is at least 2-fold greater than previously reported, and activation of the TSH receptor by an activating antibody M22 from a patient with Graves' disease led to more than 3-fold increase in HA production in both fibroblasts/preadipocytes and adipocytes. These effects were not consistently detected with the commercial ELISA using rooster comb HA as standard and suggest that fibroblasts/preadipocytes may play a more prominent role in HA remodeling in Graves' ophthalmopathy than previously appreciated. PMID:24302624

Formation of giant molecular clouds in global spiral structures: the role of orbital dynamics and cloud-cloud collisions

International Nuclear Information System (INIS)

Roberts, W.W. Jr.; Stewart, G.R.

1987-01-01

The different roles played by orbital dynamics and dissipative cloud-cloud collisions in the formation of giant molecular clouds (GMCs) in a global spiral structure are investigated. The interstellar medium (ISM) is simulated by a system of particles, representing clouds, which orbit in a spiral-perturbed, galactic gravitational field. The overall magnitude and width of the global cloud density distribution in spiral arms is very similar in the collisional and collisionless simulations. The results suggest that the assumed number density and size distribution of clouds and the details of individual cloud-cloud collisions have relatively little effect on these features. Dissipative cloud-cloud collisions play an important steadying role for the cloud system's global spiral structure. Dissipative cloud-cloud collisions also damp the relative velocity dispersion of clouds in massive associations and thereby aid in the effective assembling of GMC-like complexes

Rings of Molecular Line Emission in the Disk Orbiting the Young, Close Binary V4046 Sgr

Science.gov (United States)

Dickson-Vandervelde, Dorothy; Kastner, Joel H.; Qi, C.; Forveille, Thierry; Hily-Blant, Pierre; Oberg, Karin; Wilner, David; Andrews, Sean; Gorti, Uma; Rapson, Valerie; Sacco, Germano; Principe, David

2018-01-01

We present analysis of a suite of subarcsecond ALMA Band 6 (1.1 - 1.4 mm) molecular line images of the circumbinary, protoplanetary disk orbiting V4046 Sgr. The ~20 Myr-old V4046 Sgr system, which lies a mere ~73 pc from Earth, consists of a close (separation ~10 Rsun) pair of roughly solar-mass stars that are orbited by a gas-rich crcumbinary disk extending to ~350 AU in radius. The ALMA images reveal that the molecules CO and HCN and their isotopologues display centrally peaked surface brightness morphologies, whereas the cyanide group molecules (HC3N, CH3CN), deuterated molecules (DCN, DCO+), hydrocarbons (as traced by C2H), and potential CO ice line tracers (N2H+, and H2CO) appear as a sequence of sharp and diffuse rings of increasing radii. The characteristic sizes of these molecular emission rings, which range from ~25 to >100 AU in radius, are evident in radial emission-line surface brightness profiles extracted from the deprojected disk images. We find that emission from 13CO emission transitions from optically thin to thick within ~50 AU, whereas C18O emission remains optically thin within this radius. We summarize the insight into the physical and chemical processes within this evolved protoplanetary disk that can be obtained from comparisons of the various emission-line morphologies with each other and with that of the continuum (large-grain) emission on size scales of tens of AU.This research is supported by NASA Exoplanets program grant NNX16AB43G to RIT

Fragment molecular orbital study on electron tunneling mechanisms in bacterial photosynthetic reaction center.

Science.gov (United States)

Kitoh-Nishioka, Hirotaka; Ando, Koji

2012-11-01

The tunneling mechanisms of electron transfers (ETs) in photosynthetic reaction center of Blastochloris viridis are studied by the ab initio fragment molecular orbital (FMO) method combined with the generalized Mulliken-Hush (GMH) and the bridge Green function (GF) calculations of the electronic coupling T(DA) and the tunneling current method for the ET pathway analysis at the fragment-based resolution. For the ET from batctriopheophytin (H(L)) to menaquinone (MQ), a major tunneling current through Trp M250 and a minor back flow via Ala M215, Ala M216, and His M217 are quantified. For the ET from MQ to ubiquinone, the major tunneling pathway via the nonheme Fe(2+) and His L190 is identified as well as minor pathway via His M217 and small back flows involving His L230, Glu M232, and His M264. At the given molecular structure from X-ray experiment, the spin state of the Fe(2+) ion, its replacement by Zn(2+), or its removal are found to affect the T(DA) value by factors within 2.2. The calculated T(DA) values, together with experimentally estimated values of the driving force and the reorganization energy, give the ET rates in reasonable agreement with experiments.

Structural Characterization of MAO and Related Aluminum Complexes. 1. Solid-State 27 Al NMR with Comparison to EFG Tensors from ab Initio Molecular Orbital Calculations

Energy Technology Data Exchange (ETDEWEB)

Bryant, Pamela L.; Harwell, Chris; Mrse, Anthony A.; Emery, Earl F.; Gan, Zhedong; Caldwell, Tod; Reyes, Arneil P.; Kuhns, Philip; Hoyt, David W.; Simeral, Larry S.; Hall, Randall W.; Butler, Leslie G.

2001-11-07

Aminato and propanolato aluminum clusters with 3-, 4-, and 6-coordinate aluminum sites are studied with three 27Al NMR techniques optimized for large 27Al Quadrupole coupling constants: field-swept, frequency-stepped, and high-field MAS NMR. The 27Al quadrupole coupling constants and asymmetry parameters of molecular species, both experimental and derived from ab initio molecular orbital calculations, are correlated with structure.

Comparative molecular-orbital and atomic-orbital study of electron transfer and excitation in He++Na(3s) collisions at energies of 0.05 to 20 keV/amu

International Nuclear Information System (INIS)

Fritsch, W.; Kimura, M.; Lane, N.F.

1990-01-01

Electron transfer and excitation in 0.05- to 20-keV/amu He + +Na(3s) collisions is studied theoretically within the close-coupling method with two-electron molecular- and atomic-orbital expansion basis sets. Results agree with the trend of other information on this system. Remaining discrepancies that are larger than those in similar contemporary studies of one-electron systems are discussed with reference to the convergence of this two-electron study. Results for the integral alignment parameter A 20 are also presented as a guideline for future experimental study

Communication: Systematic shifts of the lowest unoccupied molecular orbital peak in x-ray absorption for a series of 3d metal porphyrins

DEFF Research Database (Denmark)

García Lastra, Juan Maria; Cook, P. L.; Himpsel, F. J.

2010-01-01

Porphyrins are widely used as dye molecules in solar cells. Knowing the energies of their frontier orbitals is crucial for optimizing the energy level structure of solar cells. We use near edge x-ray absorption fine structure (NEXAFS) spectroscopy to obtain the energy of the lowest unoccupied...... molecular orbital (LUMO) with respect to the N-1s core level of the molecule. A systematic energy shift of the N-1s to LUMO transition is found along a series of 3d metal octaethylporphyrins and explained by density functional theory. It is mainly due to a shift of the N-1s level rather than a shift...

Journal of Chemical Sciences | Indian Academy of Sciences

Indian Academy of Sciences (India)

The paper gives a brief account of the recently introduced Szeged index (Sz). Using this index antitubercular activities of N-2,4-difluorophenyl quinolones are subjected to quantitative structure-activity relationship analysis. The potential of Sz related to the Wiener index (W) is critically discussed. In addition, Huckel molecular ...

Molecular orbital (SCF-X-α-SW) theory of Fe2+-Mn3+, Fe3+-Mn2+, and Fe3+-Mn3+ charge transfer and magnetic exchange in oxides and silicates

Science.gov (United States)

Sherman, David M.

1990-01-01

Metal-metal charge-transfer and magnetic exchange interactions have important effects on the optical spectra, crystal chemistry, and physics of minerals. Previous molecular orbital calculations have provided insight on the nature of Fe2+-Fe3+ and Fe2+-Ti4+ charge-transfer transitions in oxides and silicates. In this work, spin-unrestricted molecular orbital calculations on (FeMnO10) clusters are used to study the nature of magnetic exchange and electron delocalization (charge transfer) associated with Fe3+-Mn2+, Fe3+-Mn3+, and Fe2+-Mn3+ interactions in oxides and silicates. 

Using Molecular Modeling to Understand Some of the More Subtle Aspects of Aromaticity and Antiaromaticity

Science.gov (United States)

Box, Vernon G. S.

2011-01-01

pi-Electron delocalization exerts one of the most significant structure or energy influences in organic chemistry. Apart from determining the shapes of alkenes and alkynes, the planarity of aromatic molecules is a hallmark of pi-electron delocalization. Huckel's rules for aromaticity are easily applied in the teaching of undergraduates, but…

Mass Transport Properties of LiD-U Mixtures from Orbital FreeMolecular Dynamics Simulations and a Pressure-Matching Mixing Rule

International Nuclear Information System (INIS)

Burakovsky, Leonid; Kress, Joel D.; Collins, Lee A.

2012-01-01

Mass transport properties for LiD-U mixtures were calculated using a pressure matching mixture rule for the mixing of LiD and of U properties simulated with Orbital Free Molecular Dynamics (OFMD). The mixing rule was checked against benchmark OFMD simulations for the fully interacting three-component (Li, D, U) system. To obtain transport coefficients for LiD-U mixtures of different (LiD) x U (1-x) compositions as functions of temperature and mixture density is a tedious task. Quantum molecular dynamics (MD) simulations can be employed, as in the case LiD or U. However, due to the presence of the heavy constituent U, such simulations proceed so slowly that only a limited number of numerical data points in the (x, ρ, T) phase space can be obtained. To finesse this difficulty, transport coefficients for a mixture can be obtained using a pressure-matching mixing rule discussed. For both LiD and U, the corresponding transport coefficients were obtained earlier from quantum molecular dynamics simulations. In these simulations, the quantum behavior of the electrons was represented using an orbital free (OF) version of density functional theory, and ions were advanced in time using classical molecular dynamics. The total pressure of the system, P = nk B T/V + P e , is the sum of the ideal gas pressure of the ions plus the electron pressure. The mass self-diffusion coefficient for species α, D α , the mutual diffusion coefficient for species α and β, Dαβ, and the shear viscosity, η, are computed from the appropriate autocorrelation function. The details of similar QMD calculations on LiH are described in Ref. [1] for 0.5 eV < T < 3 eV, and in Ref. [2] for 2 eV < T < 6 eV.

Molecular heterojunctions of oligo(phenylene ethynylene)s with linear to cruciform framework

DEFF Research Database (Denmark)

Wei, Zhongming; Hansen, Tim; Santella, Marco

2015-01-01

Electrical transport properties of molecular junctions are fundamentally affected by the energy alignment between molecular frontier orbitals (highest occupied molecular orbital (HOMO) or lowest unoccupied molecular orbital (LUMO)) and Fermi level (or work function) of electrode metals. Dithiaful......Electrical transport properties of molecular junctions are fundamentally affected by the energy alignment between molecular frontier orbitals (highest occupied molecular orbital (HOMO) or lowest unoccupied molecular orbital (LUMO)) and Fermi level (or work function) of electrode metals......-tetrathiafulvalene (TTF) can form good self-assembled monolayers (SAMs) on Au substrates. Molecular heterojunctions based on these SAMs are investigated using conducting probe-atomic force microscopy with different tips (Ag, Au, and Pt) and Fermi levels. The calibrated conductance values follow the sequence OPE3-TTF...... > OPE3-DTF > OPE3 irrespective of the tip metal. Rectification properties (or diode behavior) are observed in case of the Ag tip for which the work function is furthest from the HOMO levels of the OPE3s. Quantum chemical calculations of the transmission qualitatively agree with the experimental data...

Physical Meaning of Virtual Kohn-Sham Orbitals and Orbital Energies: An Ideal Basis for the Description of Molecular Excitations

NARCIS (Netherlands)

van Meer, R.; Gritsenko, O.V.; Baerends, E.J.

2014-01-01

In recent years, several benchmark studies on the performance of large sets of functionals in time-dependent density functional theory (TDDFT) calculations of excitation energies have been performed. The tested functionals do not approximate exact Kohn-Sham orbitals and orbital energies closely. We

Photoionization and molecular structure

International Nuclear Information System (INIS)

Palma, A.

1983-01-01

A presentation is here given of the theoretical work on photoionization and molecular structure carried out by the author and coworkers. The implications of the photoionization process on the molecular geometry are emphasized. In particular, the ionization effect on deep orbitals is considered and it is shown that, contrary to traditional thinking, these orbitals have relevant effects on the molecular geometry. The problem of calculating photoionization relative intensities for the full spectrum is also considered, and the results of the present model are compared with experimental and other theoretical results. (author)

Molecular orbital calculations of the unpaired electron distribution and electric field gradients in divalent paramagnetic Ir complexes

International Nuclear Information System (INIS)

Nogueira, S.R.; Vugman, N.V.; Guenzburger, D.

1988-01-01

Semi-empirical Molecular Orbital calculations were performed for the paramagnetic complex ions [Ir(CN) 5 ] 3- , [Ir(CN) 5 Cl] 4- and [Ir(CN) 4 Cl 2 ] 4- . Energy levels schemes and Mulliken-type populations were obtained. The distribution of the unpaired spin over the atoms in the complexes was derived, and compared to data obtained from Electron Paramagnetic Resonance spectra with the aid of a Ligand Field model. The electric field gradients at the Ir nucleus were calculated and compared to experiment. The results are discussed in terms of the chemical bonds formed by Ir and the ligands. (author) [pt

Controlling the Orbital Sequence in Individual Cu-Phthalocyanine Molecules

NARCIS (Netherlands)

Uhlmann, C.; Swart, I.; Repp, J.

2013-01-01

We report on the controlled change of the energetic ordering of molecular orbitals. Negatively charged copper(II)phthalocyanine on NaCl/Cu(100) undergoes a Jahn–Teller distortion that lifts the degeneracy of two frontier orbitals. The energetic order of the levels can be controlled by Au and Ag

Explicit polarization (X-Pol) potential using ab initio molecular orbital theory and density functional theory.

Science.gov (United States)

Song, Lingchun; Han, Jaebeom; Lin, Yen-lin; Xie, Wangshen; Gao, Jiali

2009-10-29

The explicit polarization (X-Pol) method has been examined using ab initio molecular orbital theory and density functional theory. The X-Pol potential was designed to provide a novel theoretical framework for developing next-generation force fields for biomolecular simulations. Importantly, the X-Pol potential is a general method, which can be employed with any level of electronic structure theory. The present study illustrates the implementation of the X-Pol method using ab initio Hartree-Fock theory and hybrid density functional theory. The computational results are illustrated by considering a set of bimolecular complexes of small organic molecules and ions with water. The computed interaction energies and hydrogen bond geometries are in good accord with CCSD(T) calculations and B3LYP/aug-cc-pVDZ optimizations.

Quadratically convergent algorithm for orbital optimization in the orbital-optimized coupled-cluster doubles method and in orbital-optimized second-order Møller-Plesset perturbation theory

Science.gov (United States)

Bozkaya, Uǧur; Turney, Justin M.; Yamaguchi, Yukio; Schaefer, Henry F.; Sherrill, C. David

2011-09-01

Using a Lagrangian-based approach, we present a more elegant derivation of the equations necessary for the variational optimization of the molecular orbitals (MOs) for the coupled-cluster doubles (CCD) method and second-order Møller-Plesset perturbation theory (MP2). These orbital-optimized theories are referred to as OO-CCD and OO-MP2 (or simply "OD" and "OMP2" for short), respectively. We also present an improved algorithm for orbital optimization in these methods. Explicit equations for response density matrices, the MO gradient, and the MO Hessian are reported both in spin-orbital and closed-shell spin-adapted forms. The Newton-Raphson algorithm is used for the optimization procedure using the MO gradient and Hessian. Further, orbital stability analyses are also carried out at correlated levels. The OD and OMP2 approaches are compared with the standard MP2, CCD, CCSD, and CCSD(T) methods. All these methods are applied to H2O, three diatomics, and the O_4^+ molecule. Results demonstrate that the CCSD and OD methods give nearly identical results for H2O and diatomics; however, in symmetry-breaking problems as exemplified by O_4^+, the OD method provides better results for vibrational frequencies. The OD method has further advantages over CCSD: its analytic gradients are easier to compute since there is no need to solve the coupled-perturbed equations for the orbital response, the computation of one-electron properties are easier because there is no response contribution to the particle density matrices, the variational optimized orbitals can be readily extended to allow inactive orbitals, it avoids spurious second-order poles in its response function, and its transition dipole moments are gauge invariant. The OMP2 has these same advantages over canonical MP2, making it promising for excited state properties via linear response theory. The quadratically convergent orbital-optimization procedure converges quickly for OMP2, and provides molecular properties that

AB INITIO molecular orbital studies of some high temperature metal halide complexes

International Nuclear Information System (INIS)

Curtiss, L.A.

1978-01-01

The use of ab initio molecular orbital calculations to aid in the characterization, i.e., structures and energies, of metal halide complexes present in high temperature salt vapors has been investigated. Standard LCAO-SCF methods were used and calculations were carried out using the minimal STO-3G basis set. The complexes included in this study were Al 2 F 6 , Al 2 Cl 6 , AlF 3 NH 3 , AlCl 3 NH 3 , and AlF 3 N 2 . The Al 2 X 6 complexes are found to have D/sub 2h/ symmetry in agreement with most experimental results. A planar form was found to be considerably higher in energy. The AlX 3 NH 3 complexes are found to have C/sub 3v/ symmetry with a small barrier to rotation about the Al-N axis. The AlF 3 N 2 complex is found to be weakly bound together with a binding energy of -8.2 kcal/mole at the STO-3G level

Illustrating Concepts in Physical Organic Chemistry with 3D Printed Orbitals

Science.gov (United States)

Robertson, Michael J.; Jorgensen, William L.

2015-01-01

Orbital theory provides a powerful tool for rationalizing and understanding many phenomena in chemistry. In most introductory chemistry courses, students are introduced to atomic and molecular orbitals in the form of two-dimensional drawings. In this work, we describe a general method for producing 3D printing files of orbital models that can be…

Positron-attachment to small molecules: Vibrational enhancement of positron affinities with configuration interaction level of multi-component molecular orbital approach

Energy Technology Data Exchange (ETDEWEB)

Tachikawa, Masanori [Quantum Chemistry Division, Graduate School of NanoBioScience, Yokohama City University, 22-2 Seto, Kanazawa, Yokohama 236-0027 (Japan)

2015-12-31

To theoretically demonstrate the binding of a positron to small polarized molecules, we have calculated the vibrational averaged positron affinity (PA) values along the local vibrational contribution with the configuration interaction level of multi-component molecular orbital method. This method can take the electron-positron correlation contribution into account through single electronic - single positronic excitation configurations. The PA values are enhanced by including the local vibrational contribution from vertical PA values due to the anharmonicity of the potential.

Evaluation of electronic states of implanted materials by molecular orbital calculation

International Nuclear Information System (INIS)

Saito, Jun-ichi; Kano, Shigeki

1997-07-01

In order to understand the effect of implanted atom in ceramics and metals on the sodium corrosion, the electronic structures of un-implanted and implanted materials were calculated using DV-Xα cluster method which was one of molecular orbital calculations. The calculated materials were β-Si 3 N 4 , α-SiC and β-SiC as ceramics, and f.c.c. Fe, b.c.c. Fe and b.c.c. Nb as metals. An Fe, Mo and Hf atom for ceramics, and N atom for metals were selected as implanted atoms. Consequently, it is expected that the corrosion resistance of β-Si 3 N 4 is improved, because the ionic bonding reduced by the implantation. When the implanted atom is occupied at interstitial site in α-SiC and β-SiC, the ionic bonding reduced. Hence, there is a possibility to improve the corrosion resistance of α-SiC and β-SiC. It is clear that Hf is most effective element among implanted atoms in this study. As the covalent bond between N atom and surrounding Fe atoms increased largely in f.c.c. Fe by N implantation, it was expected that the corrosion resistance of f.c.c. Fe improved in liquid sodium. (J.P.N.)

Atomic-orbital expansion model for describing ion-atom collisions at intermediate and low energies

International Nuclear Information System (INIS)

Lin, C.D.; Fritsch, W.

1983-01-01

In the description of inelastic processes in ion-atom collisions at moderate energies, the semiclassical close-coupling method is well established as the standard method. Ever since the pioneering work on H + + H in the early 60's, the standard procedure is to expand the electronic wavefunction in terms of molecular orbitals (MO) or atomic orbitals (AO) for describing collisions at, respectively, low or intermediate velocities. It has been recognized since early days that traveling orbitals are needed in the expansions in order to represent the asymptotic states in the collisions correctly. While the adoption of such traveling orbitals presents no conceptual difficulties for expansions using atomic orbitals, the situation for molecular orbitals is less clear. In recent years, various forms of traveling MO's have been proposed, but conflicting results for several well-studied systems have been reported

Calculation of wave-functions with frozen orbitals in mixed quantum mechanics/molecular mechanics methods. Part I. Application of the Huzinaga equation.

Science.gov (United States)

Ferenczy, György G

2013-04-05

Mixed quantum mechanics/quantum mechanics (QM/QM) and quantum mechanics/molecular mechanics (QM/MM) methods make computations feasible for extended chemical systems by separating them into subsystems that are treated at different level of sophistication. In many applications, the subsystems are covalently bound and the use of frozen localized orbitals at the boundary is a possible way to separate the subsystems and to ensure a sensible description of the electronic structure near to the boundary. A complication in these methods is that orthogonality between optimized and frozen orbitals has to be warranted and this is usually achieved by an explicit orthogonalization of the basis set to the frozen orbitals. An alternative to this approach is proposed by calculating the wave-function from the Huzinaga equation that guaranties orthogonality to the frozen orbitals without basis set orthogonalization. The theoretical background and the practical aspects of the application of the Huzinaga equation in mixed methods are discussed. Forces have been derived to perform geometry optimization with wave-functions from the Huzinaga equation. Various properties have been calculated by applying the Huzinaga equation for the central QM subsystem, representing the environment by point charges and using frozen strictly localized orbitals to connect the subsystems. It is shown that a two to three bond separation of the chemical or physical event from the frozen bonds allows a very good reproduction (typically around 1 kcal/mol) of standard Hartree-Fock-Roothaan results. The proposed scheme provides an appropriate framework for mixed QM/QM and QM/MM methods. Copyright © 2012 Wiley Periodicals, Inc.

Ab initio molecular orbital calculations on the associated complexes of lithium cyanide with ammonia

International Nuclear Information System (INIS)

Mohandas, P.; Shivaglal, M.C.; Chandrasekhar, J.

1995-01-01

Ab initio molecular orbital (MO) calculations with the 3-21G and 6-31G basis sets are carried out on a series of complexes of NH 3 with Li + , C triple-bond N - , LiCN, and its isomer LiNC. The BSSE-corrected interaction energies, geometrical parameters, internal force constants, and harmonic vibrational frequencies are evaluated for 15 species. Complexes with trifurcated (C 3v ) structures are calculated to be saddle points on the potential energy surfaces and have one imaginary frequency each. Calculated energies, geometrical parameters, internal force constants, and harmonic vibrational frequencies of the various species considered are discussed in terms of the nature of association of LiCN with ammonia. The vibrational frequencies of the relevant complexed species are compared with the experimental frequencies reported earlier for solutions of lithium cyanide in liquid ammonia. 40 refs., 1 fig., 4 tabs

Orbital free ab initio molecular dynamics simulation study of some static and dynamic properties of liquid noble metals

Directory of Open Access Journals (Sweden)

G.M. Bhuiyan

2012-10-01

Full Text Available Several static and dynamic properties of liquid Cu, Ag and Au at thermodynamic states near their respective melting points, have been evaluated by means of the orbital free ab-initio molecular dynamics simulation method. The calculated static structure shows good agreement with the available X-ray and neutron diffraction data. As for the dynamic properties, the calculated dynamic structure factors point to the existence of collective density excitations along with a positive dispersion for l-Cu and l-Ag. Several transport coefficients have been obtained which show a reasonable agreement with the available experimental data.

Electronic Rydberg wavepacket effects on molecular vibration

International Nuclear Information System (INIS)

Hughes, I.G.; Meacher, D.R.

1994-01-01

Electronic wavepacket states of molecular hydrogen are considered which represent the situation of a spectator electron orbiting a molecular core. A quantum defect theory approach is used to determine the energy level structure, wavefunctions and molecular potentials, which is valid in regions where the quantum defects approach zero. In such a region the orbital motion of the wavepacket leads to a periodic variation in the molecular vibration frequency of the order of 100 cm -1 . Possible detection schemes are discussed. (author)

Spin-Orbit Effect on the Molecular Properties of TeXn (X = F, Cl, Br, and I; n = 1, 2, and 4): A Density Functional Theory and Ab Initio Study.

Science.gov (United States)

Moon, Jiwon; Kim, Joonghan

2016-09-29

Density functional theory (DFT) and ab initio calculations, including spin-orbit coupling (SOC), were performed to investigate the spin-orbit (SO) effect on the molecular properties of tellurium halides, TeXn (X = F, Cl, Br, and I; n = 1, 2, and 4). SOC elongates the Te-X bond and slightly reduces the vibrational frequencies. Consideration of SOC leads to better agreement with experimental values. Møller-Plesset second-order perturbation theory (MP2) seriously underestimates the Te-X bond lengths. In contrast, B3LYP significantly overestimates them. SO-PBE0 and multireference configuration interactions with the Davidson correction (MRCI+Q), which include SOC via a state-interaction approach, give the Te-I bond length of TeI2 that matches the experimental value. On the basis of the calculated thermochemical energy and optimized molecular structure, TeI4 is unlikely to be stable. The use of PBE0 including SOC is strongly recommended for predicting the molecular properties of Te-containing compounds.

16O + 16O + valence neutrons in molecular orbitals structures of positive- and negative-parity superdeformed bands in 34S

International Nuclear Information System (INIS)

Taniguchi, Yasutaka

2015-01-01

The structures of superdeformed (SD) states in 34 S have been investigated using the antisymmetrized molecular dynamics and generator coordinate method (GCM). The GCM basis wave functions are calculated via energy variation with a constraint on the quadrupole deformation parameter β. By applying the GCM after parity and angular momentum projections, the coexistence of two positive- and one negative-parity SD bands are predicted, and low-lying states and other deformed bands are obtained. The SD bands have structures of 16 O + 16 O + two valence neutrons in molecular orbitals around the two 16 O cores in a cluster picture. The configurations of the two valence neutrons are δ 2 and π 2 for the positive-parity SD bands and π 1 δ 1 for the negative-parity SD band. (author)

16O + 16O + valence neutrons in molecular orbitals structures of positive- and negative-parity superdeformed bands in 34S

International Nuclear Information System (INIS)

Taniguchi, Yasutaka

2014-01-01

The structures of superdeformed (SD) states in 34 S are investigated using the antisymmetrized molecular dynamics and generator coordinate method (GCM). The GCM basis wave functions are calculated via energy variation with a constraint on the quadrupole deformation parameter β. By applying the GCM after parity and angular momentum projections, the coexistence of two positive- and one negative-parity SD bands are predicted, and low-lying states and other deformed bands are obtained. The SD bands have structures of 16 O + 16 O + two valence neutrons in molecular orbitals around the two 16 O cores in a cluster picture. The configurations of the two valence neutrons are δ 2 and π 2 for the positive-parity SD bands and π 1 δ 1 for the negative-parity SD band

Nonadiabatic electron wavepacket dynamics behind molecular autoionization

Science.gov (United States)

Matsuoka, Takahide; Takatsuka, Kazuo

2018-01-01

A theoretical method for real-time dynamics of nonadiabatic reorganization of electronic configurations in molecules is developed, with dual aim that the intramolecular electron dynamics can be probed by means of direct and/or indirect photoionizations and that the physical origins behind photoionization signals attained in the time domain can be identified in terms of the language of time-dependent quantum chemistry. In doing so, we first formulate and implement a new computational scheme for nonadiabatic electron dynamics associated with molecular ionization, which well fits in the general theory of nonadiabatic electron dynamics. In this method, the total nonadiabatic electron wavepackets are propagated in time directly with complex natural orbitals without referring to Hartree-Fock molecular orbitals, and the amount of electron flux from a molecular region leading to ionization is evaluated in terms of the relevant complex natural orbitals. In the second half of this paper, we apply the method to electron dynamics in the elementary processes consisting of the Auger decay to demonstrate the methodological significance. An illustrative example is taken from an Auger decay starting from the 2a1 orbital hole-state of H2O+. The roles of nuclear momentum (kinetic) couplings in electronic-state mixing during the decay process are analyzed in terms of complex natural orbitals, which are schematically represented in the conventional language of molecular symmetry of the Hartree-Fock orbitals.

Ultrafast molecular imaging by laser-induced electron diffraction

International Nuclear Information System (INIS)

Peters, M.; Nguyen-Dang, T. T.; Cornaggia, C.; Saugout, S.; Charron, E.; Keller, A.; Atabek, O.

2011-01-01

We address the feasibility of imaging geometric and orbital structures of a polyatomic molecule on an attosecond time scale using the laser-induced electron diffraction (LIED) technique. We present numerical results for the highest molecular orbitals of the CO 2 molecule excited by a near-infrared few-cycle laser pulse. The molecular geometry (bond lengths) is determined within 3% of accuracy from a diffraction pattern which also reflects the nodal properties of the initial molecular orbital. Robustness of the structure determination is discussed with respect to vibrational and rotational motions with a complete interpretation of the laser-induced mechanisms.

Orbital momentum profiles and binding energy spectra for the complete valence shell of molecular fluorine

Energy Technology Data Exchange (ETDEWEB)

Zheng, Y.; Brion, C.E. [British Columbia Univ., Vancouver, BC (Canada). Dept. of Chemistry; Brunger, M.J.; Zhao, K.; Grisogono, A.M.; Braidwood, S.; Weigold, E. [Flinders Univ. of South Australia, Adelaide, SA (Australia). Electronic Structure of Materials Centre; Chakravorty, S.J.; Davidson, E.R. [Indiana Univ., Bloomington, IN (United States). Dept. of Chemistry; Sgamellotti, A. [Univ di Perugia (Italy). Dipartimento di Chimica; von Niessen, W. [Technische Univ. Braunschweig (Germany). Inst fuer Physikalische

1996-01-01

The first electronic structural study of the complete valence shell binding energy spectrum of molecular fluorine, encompassing both the outer and inner valence regions, is reported. These binding energy spectra as well as the individual orbital momentum profiles have been measured using an energy dispersive multichannel electron momentum spectrometer at a total energy of 1500 eV, with an energy resolution of 1.5 eV and a momentum resolution of 0.1 a.u. The measured binding energy spectra in the energy range of 14-60 eV are compared with the results of ADC(4) many-body Green`s function and also direct-Configuration Interaction (CI) and MRSD-CI calculations. The experimental orbital electron momentum profiles are compared with SCF theoretical profiles calculated using the target Hartree-Fock approximation with a range of basis sets and with Density Functional Theory predictions in the target Kohn-Sham approximation with non-local potentials. The truncated (aug-cc-pv5z) Dunning basis sets were used for the Density Functional Theory calculations which also include some treatment of correlation via the exchange and correlation potentials. Comparisons are also made with the full ion-neutral overlap amplitude calculated with MRSD-CI wave functions. Large, saturated basis sets (199-GTO) were employed for both the high level SCF near Hartree-Fock limit and MRSD-CI calculations to investigate the effects of electron correlation and relaxation. 66 refs., 9 tabs., 9 figs.

Orbital momentum profiles and binding energy spectra for the complete valence shell of molecular fluorine

International Nuclear Information System (INIS)

Zheng, Y.; Brion, C.E.; Brunger, M.J.; Zhao, K.; Grisogono, A.M.; Braidwood, S.; Weigold, E.; Chakravorty, S.J.; Davidson, E.R.; Sgamellotti, A.; von Niessen, W.

1996-01-01

The first electronic structural study of the complete valence shell binding energy spectrum of molecular fluorine, encompassing both the outer and inner valence regions, is reported. These binding energy spectra as well as the individual orbital momentum profiles have been measured using an energy dispersive multichannel electron momentum spectrometer at a total energy of 1500 eV, with an energy resolution of 1.5 eV and a momentum resolution of 0.1 a.u. The measured binding energy spectra in the energy range of 14-60 eV are compared with the results of ADC(4) many-body Green's function and also direct-Configuration Interaction (CI) and MRSD-CI calculations. The experimental orbital electron momentum profiles are compared with SCF theoretical profiles calculated using the target Hartree-Fock approximation with a range of basis sets and with Density Functional Theory predictions in the target Kohn-Sham approximation with non-local potentials. The truncated (aug-cc-pv5z) Dunning basis sets were used for the Density Functional Theory calculations which also include some treatment of correlation via the exchange and correlation potentials. Comparisons are also made with the full ion-neutral overlap amplitude calculated with MRSD-CI wave functions. Large, saturated basis sets (199-GTO) were employed for both the high level SCF near Hartree-Fock limit and MRSD-CI calculations to investigate the effects of electron correlation and relaxation. 66 refs., 9 tabs., 9 figs

Calculation of wave-functions with frozen orbitals in mixed quantum mechanics/molecular mechanics methods. II. Application of the local basis equation.

Science.gov (United States)

Ferenczy, György G

2013-04-05

The application of the local basis equation (Ferenczy and Adams, J. Chem. Phys. 2009, 130, 134108) in mixed quantum mechanics/molecular mechanics (QM/MM) and quantum mechanics/quantum mechanics (QM/QM) methods is investigated. This equation is suitable to derive local basis nonorthogonal orbitals that minimize the energy of the system and it exhibits good convergence properties in a self-consistent field solution. These features make the equation appropriate to be used in mixed QM/MM and QM/QM methods to optimize orbitals in the field of frozen localized orbitals connecting the subsystems. Calculations performed for several properties in divers systems show that the method is robust with various choices of the frozen orbitals and frontier atom properties. With appropriate basis set assignment, it gives results equivalent with those of a related approach [G. G. Ferenczy previous paper in this issue] using the Huzinaga equation. Thus, the local basis equation can be used in mixed QM/MM methods with small size quantum subsystems to calculate properties in good agreement with reference Hartree-Fock-Roothaan results. It is shown that bond charges are not necessary when the local basis equation is applied, although they are required for the self-consistent field solution of the Huzinaga equation based method. Conversely, the deformation of the wave-function near to the boundary is observed without bond charges and this has a significant effect on deprotonation energies but a less pronounced effect when the total charge of the system is conserved. The local basis equation can also be used to define a two layer quantum system with nonorthogonal localized orbitals surrounding the central delocalized quantum subsystem. Copyright © 2013 Wiley Periodicals, Inc.

Internal rotation of 1-Aryl-3,3-dialkyltriazenes. Comparison of semiempirical molecular orbital calculations with far-infrared, Raman, and NMR spectroscopic results

International Nuclear Information System (INIS)

Panitz, J.C.; Lippert, T.; Wokaun, A.

1994-01-01

PM3 and AM1 semiempirical molecular orbital techniques are used to establish a model for internal rotation about the N 2 -N 3 axis of 1-aryl-3,3-dialkyltriazines. The PM3 method is satisfactory for obtaining agreement between the experimental and calculated results, but the AM1 method has an artifact in the potential energy curve of internal rotation about the N 2 -N 3 axis. 24 refs., 6 figs., 5 tabs

Ionization equilibrium and equation of state in the solar interior

International Nuclear Information System (INIS)

Rogers, F.J.

1984-01-01

Many-body formulations of the equations of state are restated as a set of Saha-like equations. It is shown that the resulting equations are unique and convergent. These equations are similar to the usual Saha equations to the order of the Debye-Huckel theory. Higher order corrections, however, require a more general formulation. It is demonstrated that the positive free energy resulting from the interaction of unscreened particles in high orbits depletes the occupation of these states, without the introduction of shifted energy levels

Introducing a new bond reactivity index: Philicities for natural bond orbitals.

Science.gov (United States)

Sánchez-Márquez, Jesús; Zorrilla, David; García, Víctor; Fernández, Manuel

2017-12-22

In the present work, a new methodology defined for obtaining reactivity indices (philicities) is proposed. This is based on reactivity functions such as the Fukui function or the dual descriptor, and makes it possible to project the information from reactivity functions onto molecular orbitals, instead of onto the atoms of the molecule (atomic reactivity indices). The methodology focuses on the molecules' natural bond orbitals (bond reactivity indices) because these orbitals have the advantage of being localized, allowing the reaction site of an electrophile or nucleophile to be determined within a very precise molecular region. This methodology provides a "philicity" index for every NBO, and a representative set of molecules has been used to test the new definition. A new methodology has also been developed to compare the "finite difference" and the "frontier molecular orbital" approximations. To facilitate their use, the proposed methodology as well as the possibility of calculating the new indices have been implemented in a new version of UCA-FUKUI software. In addition, condensation schemes based on atomic populations of the "atoms in molecules" theory, the Hirshfeld population analysis, the approximation of Mulliken (with a minimal basis set) and electrostatic potential-derived charges have also been implemented, including the calculation of "bond reactivity indices" defined in previous studies. Graphical abstract A new methodology defined for obtaining bond reactivity indices (philicities) is proposed and makes it possible to project the information from reactivity functions onto molecular orbitals. The proposed methodology as well as the possibility of calculating the new indices have been implemented in a new version of UCA-FUKUI software. In addition, this version can use new atomic condensation schemes and new "utilities" have also been included in this second version.

Image-charge-induced localization of molecular orbitals at metal-molecule interfaces

DEFF Research Database (Denmark)

Strange, M.; Thygesen, K. S.

2012-01-01

Quasiparticle (QP) wave functions, also known as Dyson orbitals, extend the concept of single-particle states to interacting electron systems. Here we employ many-body perturbation theory in the GW approximation to calculate the QP wave functions for a semiempirical model describing a pi-conjugat......Quasiparticle (QP) wave functions, also known as Dyson orbitals, extend the concept of single-particle states to interacting electron systems. Here we employ many-body perturbation theory in the GW approximation to calculate the QP wave functions for a semiempirical model describing a pi...

Experimental investigation of the EPR parameters and molecular orbital bonding coefficients for VO{sup 2+} ion in NaH{sub 2}PO{sub 4}·2H{sub 2}O single crystals

Energy Technology Data Exchange (ETDEWEB)

Kalfaoğlu, Emel [Ondokuz Mayıs University, Faculty of Sciences, Department of Physics, 55139 Kurupelit-Samsun (Turkey); Karabulut, Bünyamin, E-mail: bbulut@omu.edu.tr [Ondokuz Mayıs University, Faculty of Engineering, Department of Computer Engineering, 55139 Kurupelit-Samsun (Turkey)

2016-09-15

Electron paramagnetic resonance (EPR) spectra of VO{sup 2+} ions in NaH{sub 2}PO{sub 4}·2H{sub 2}O single crystal have been studied. The spin-Hamiltonian parameters and molecular orbital bonding coefficients were calculated. The angular variation of the EPR spectra shows two different VO{sup 2+} complexes. These are located in different chemical environment and each environment contains four magnetically inequivalent VO{sup 2+} sites. The crystal field around VO{sup 2+} ion is approximately axially symmetric since a strong V=O bond distorts the crystal lattice. Spin Hamiltonian parameters and molecular orbital bonding coefficients were calculated from the EPR data and the nature of bonding in the complex was discussed together.

A geometric initial guess for localized electronic orbitals in modular biological systems

Energy Technology Data Exchange (ETDEWEB)

Beckman, P. G. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Univ. of Chicago, IL (United States); Fattebert, J. L. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Lau, E. Y. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Osei-Kuffuor, D. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

2017-09-11

Recent first-principles molecular dynamics algorithms using localized electronic orbitals have achieved O(N) complexity and controlled accuracy in simulating systems with finite band gaps. However, accurately deter- mining the centers of these localized orbitals during simulation setup may require O(N³) operations, which is computationally infeasible for many biological systems. We present an O(N) approach for approximating orbital centers in proteins, DNA, and RNA which uses non-localized solutions for a set of fixed-size subproblems to create a set of geometric maps applicable to larger systems. This scalable approach, used as an initial guess in the O(N) first-principles molecular dynamics code MGmol, facilitates first-principles simulations in biological systems of sizes which were previously impossible.

Tracking the ultrafast motion of a single molecule by femtosecond orbital imaging

Science.gov (United States)

Cocker, Tyler L.; Peller, Dominik; Yu, Ping; Repp, Jascha; Huber, Rupert

2016-11-01

Watching a single molecule move on its intrinsic timescale has been one of the central goals of modern nanoscience, and calls for measurements that combine ultrafast temporal resolution with atomic spatial resolution. Steady-state experiments access the requisite spatial scales, as illustrated by direct imaging of individual molecular orbitals using scanning tunnelling microscopy or the acquisition of tip-enhanced Raman and luminescence spectra with sub-molecular resolution. But tracking the intrinsic dynamics of a single molecule directly in the time domain faces the challenge that interactions with the molecule must be confined to a femtosecond time window. For individual nanoparticles, such ultrafast temporal confinement has been demonstrated by combining scanning tunnelling microscopy with so-called lightwave electronics, which uses the oscillating carrier wave of tailored light pulses to directly manipulate electronic motion on timescales faster even than a single cycle of light. Here we build on ultrafast terahertz scanning tunnelling microscopy to access a state-selective tunnelling regime, where the peak of a terahertz electric-field waveform transiently opens an otherwise forbidden tunnelling channel through a single molecular state. It thereby removes a single electron from an individual pentacene molecule’s highest occupied molecular orbital within a time window shorter than one oscillation cycle of the terahertz wave. We exploit this effect to record approximately 100-femtosecond snapshot images of the orbital structure with sub-ångström spatial resolution, and to reveal, through pump/probe measurements, coherent molecular vibrations at terahertz frequencies directly in the time domain. We anticipate that the combination of lightwave electronics and the atomic resolution of our approach will open the door to visualizing ultrafast photochemistry and the operation of molecular electronics on the single-orbital scale.

Effective convergence to complete orbital bases and to the atomic Hartree--Fock limit through systematic sequences of Gaussian primitives

International Nuclear Information System (INIS)

Schmidt, M.W.; Ruedenberg, K.

1979-01-01

Optimal starting points for expanding molecular orbitals in terms of atomic orbitals are the self-consistent-field orbitals of the free atoms and accurate information about the latter is essential for the construction of effective AO bases for molecular calculations. For expansions of atomic SCF orbitals in terms of Gaussian primitives, which are of particular interest for applications in polyatomic quantum chemistry, previous information has been limited in accuracy. In the present investigation a simple procedure is given for finding expansions of atomic self-consistent-field orbitals in terms of Gaussian primitives to arbitrarily high accuracy. The method furthermore opens the first avenue so far for approaching complete basis sets through systematic sequences of atomic orbitals

3D Printing of Molecular Models with Calculated Geometries and p Orbital Isosurfaces

Science.gov (United States)

Carroll, Felix A.; Blauch, David N.

2017-01-01

3D printing was used to prepare models of the calculated geometries of unsaturated organic structures. Incorporation of p orbital isosurfaces into the models enables students in introductory organic chemistry courses to have hands-on experience with the concept of orbital alignment in strained and unstrained p systems.

Frontier molecular orbitals of a single molecule adsorbed on thin insulating films supported by a metal substrate: electron and hole attachment energies.

Science.gov (United States)

Scivetti, Iván; Persson, Mats

2017-09-06

We present calculations of vertical electron and hole attachment energies to the frontier orbitals of a pentacene molecule absorbed on multi-layer sodium chloride films supported by a copper substrate using a simplified density functional theory (DFT) method. The adsorbate and the film are treated fully within DFT, whereas the metal is treated implicitly by a perfect conductor model. We find that the computed energy gap between the highest and lowest unoccupied molecular orbitals-HOMO and LUMO -from the vertical attachment energies increases with the thickness of the insulating film, in agreement with experiments. This increase of the gap can be rationalised in a simple dielectric model with parameters determined from DFT calculations and is found to be dominated by the image interaction with the metal. We find, however, that this simplified model overestimates the downward shift of the energy gap in the limit of an infinitely thick film.

Proposed alteration of images of molecular orbitals obtained using a scanning tunneling microscope as a probe of electron correlation.

Science.gov (United States)

Toroz, Dimitrios; Rontani, Massimo; Corni, Stefano

2013-01-04

Scanning tunneling spectroscopy (STS) allows us to image single molecules decoupled from the supporting substrate. The obtained images are routinely interpreted as the square moduli of molecular orbitals, dressed by the mean-field electron-electron interaction. Here we demonstrate that the effect of electron correlation beyond the mean field qualitatively alters the uncorrelated STS images. Our evidence is based on the ab initio many-body calculation of STS images of planar molecules with metal centers. We find that many-body correlations alter significantly the image spectral weight close to the metal center of the molecules. This change is large enough to be accessed experimentally, surviving to molecule-substrate interactions.

Investigation of the molecular conformations of ethanol using electron momentum spectroscopy

International Nuclear Information System (INIS)

Ning, C G; Luo, Z H; Huang, Y R; Liu, K; Zhang, S F; Deng, J K; Hajgato, B; Morini, F; Deleuze, M S

2008-01-01

The valence electronic structure and momentum-space electron density distributions of ethanol have been investigated with our newly constructed high-resolution electron momentum spectrometer. The measurements are compared to thermally averaged simulations based on Kohn-Sham (B3LYP) orbital densities as well as one-particle Green's function calculations of ionization spectra and Dyson orbital densities, assuming Boltzmann's statistical distribution of the molecular structure over the two energy minima defining the anti and gauche conformers. One-electron ionization energies and momentum distributions in the outer-valence region were found to be highly dependent upon the molecular conformation. Calculated momentum distributions indeed very sensitively reflect the distortions and topological changes that molecular orbitals undergo due to the internal rotation of the hydroxyl group, and thereby exhibit variations which can be traced experimentally. The B3LYP model Kohn-Sham orbital densities are overall in good agreement with the experimental distributions, and closely resemble benchmark ADC(3) Dyson orbital densities. Both approaches fail to quantitatively reproduce the experimental momentum distributions characterizing the highest occupied molecular orbital. Since electron momentum spectroscopy measurements at various electron impact energies indicate that the plane wave impulse approximation is valid, this discrepancy between theory and experiment is tentatively ascribed to thermal disorder, i.e. large-amplitude and thermally induced dynamical distortions of the molecular structure in the gas phase

Metal-metal bonds involving the f elements. 4. Molecular orbital studies of metal-metal and metal-ligand interactions in dinuclear uranium(V) systems

International Nuclear Information System (INIS)

Cayton, R.H.; Novo-Gradac, K.J.; Bursten, B.E.

1991-01-01

The electronic structures of a series of dinuclear uranium(V) complexes have been investigated using Xα-SW molecular orbital calculations including quasirelativistic corrections. Complexes of the formula U 2 H 10 and U 2 (OH) 10 were used to model the metal-ligand σ and π interactions, respectively, in the known species U 2 (O-i-Pr) 10 . Two basic geometries were investigated: a vertex-sharing bioctahedron with only terminal ligands (D 4h symmetry) and an edge-sharing bioctahedron containing two bridging ligands (D 2h symmetry). The latter geometry, which is that of U 2 (O-i-Pr) 10 , was also examined at U-U bonding and nonbonding distances. The calculations indicate that the U-U interactions are significantly perturbed when H is replaced by OH, owing to strong donation from the OH pπ orbitals into selected U 5f orbitals. The result is a lack of any appreciable U-U interaction for U 2 (OH) 10 in either the D 4h or D 2h geometry. In addition, the overall OH π donation to the U 5f levels is enhanced in the D 2h geometry. The electronic structure of a hypothetical U(V) dimer, Cp 2 U 2 O 4 , was also examined in both bridged and unsupported geometries. The unbridged geometry, like that for U 2 (OH) 10 , suffered from a destabilization of the U-U σ orbital due to ligand π donation and revealed no net U-U bonding. However, the geometry exhibiting two bridging oxo ligands maintains the U-U σ-bonding MO as its lowest energy U 5f orbital. 21 refs., 8 figs., 8 tabs

Optical, thermal and electrical properties of polybenzimidazoles derived from substituted benzimidazoles

Science.gov (United States)

Anand, Siddeswaran; Muthusamy, Athianna

2017-11-01

Three benzimidazole monomers synthesized by condensing various substituted phenolic aldehydes with 4-methylphenylenediamine were converted in to polymers by oxidative polycondensation. The structure of the monomers and polymers were confirmed by various spectroscopic techniques. Electronic distribution of molecular frontier orbitals and optimized geometries of monomers were calculated by Gaussian 09 package. The spectral results showed that the repeating units are connected through both Csbnd C and Csbnd Osbnd C linkages. Both polymers and monomers are showing good fluorescence emission in blue region. The electrical conductivity of I2 doped PBIs was measured using two point probe technique. The conductivities of PBIs were compared on the basis of the charge densities obtained from Huckel method on imidazole nitrogen which is involved in iodine coordination. The conductivity of polymers increases with increase in iodine vapour contact time. The dielectric properties of the synthesized polymers have been investigated at different temperature and frequency. Among the PBIs, PBIOP is having greater thermal stability and is shown by high carbines residues of around 50% at 500 °C in thermogravimetric analysis.

Ab initio molecular-orbital study on electron correlation effects in CuO6 clusters relating to high-Tc superconductivity

International Nuclear Information System (INIS)

Yamamoto, S.; Yamaguchi, K.; Nasu, K.

1990-01-01

Ab initio molecular-orbital calculations for CuO 6 clusters have been performed to elucidate the electronic structures of undoped and doped copper oxides, which are of current interest in relation to high-T c superconductivity. The electron correlation effects for these species are thoroughly investigated by the full-valence configuration-interaction method and the complete-active-space self-consistent-field method. The electron correlation effect is relatively simple for the A g state (σ hole), whereas pair excitations and spin-flip excitations give sizable contributions to the configuration-interaction wave function for the B state (in-plane π hole). Implications of these results are discussed in relation to the mechanisms of the high-T c superconductivity

QED effects on individual atomic orbital energies

Science.gov (United States)

Kozioł, Karol; Aucar, Gustavo A.

2018-04-01

Several issues, concerning QED corrections, that are important in precise atomic calculations are presented. The leading QED corrections, self-energy and vacuum polarization, to the orbital energy for selected atoms with 30 ≤ Z ≤ 118 have been calculated. The sum of QED and Breit contributions to the orbital energy is analyzed. It has been found that for ns subshells the Breit and QED contributions are of comparative size, but for np and nd subshells the Breit contribution takes a major part of the QED+Breit sum. It has also, been found that the Breit to leading QED contributions ratio for ns subshells is almost independent of Z. The Z-dependence of QED and Breit+QED contributions per subshell is shown. The fitting coefficients may be used to estimate QED effects on inner molecular orbitals. We present results of our calculations for QED contributions to orbital energy of valence ns-subshell for group 1 and 11 atoms and discuss about the reliability of these numbers by comparing them with experimental first ionization potential data.

Measurement of the ionization probability of the 1s sigma molecular orbital in half a collision at zero impact parameter

International Nuclear Information System (INIS)

Chemin, J.F.; Andriamonje, S.; Guezet, D.; Thibaud, J.P.; Aguer, P.; Hannachi, F.; Bruandet, J.F.

1984-01-01

We have measured, for the first time, the ionization probability Psub(1s sigma) of the 1s sigma molecular orbital in the way into a nuclear reaction (in half a collision at zero impact parameter) in a near symmetric collision 58 Ni + 54 Fe at 230 MeV leads to a compound nucleus of 112 Xe highly excited which decays first by sequential emission of charged particles and then by sequential emission of gamma rays. The determination of Psub(1s sigma) is based on the coincidence measurement between X-rays and γ-rays and the Doppler shift method is used to discrimine the ''atomic'' and ''nuclear'' X-rays

Natural bond orbital analysis of molecular interactions: Theoretical study of W(CO)5 complexes with E(PH3)2 and NHEMe ligands (E=C, Si, Ge, Sn, Pb)

International Nuclear Information System (INIS)

Nguyen Thi Ai Nhung; Huynh Thi Phuong Loan; Duong Tuan Quang; Pham Van Tat

2014-01-01

The complexes with ligands carbodiphosphorane-analogues (called tetrylones) [(CO) 5 W-{E(PH 3 ) 2 }] (W5-EP 2 ) and N-heterocyclic carbene-analogues (called tetrylenes) [(CO) 5 W-{NHE Me }] (W5-NHE Me ) when E=C-Pb have been studied using natural bond orbital (NBO) method. The NBO analysis provides a consistent picture of the chemical bonding is two entire families of transition metal complexes of tetrylone and tetrylene ligands in term of donor-acceptor interactions, showing the correlation of these interactions with Wiberg bond indies (WBI), natural partial charges, and the energetically highest lying occupied molecular orbitals for σ and π orbitals of free ligands E(PH 3 ) 2 and NHE Me . Analysis of the bonding situation reveals that in E(PH 3 ) 2 and NHE Me ligands, the energy level of the π orbital rises, whereas that of the σ orbital decreases as atom E becomes heavier. The complexes with head-on-bonded ligands have (CO) 5 W←E donation which comes from the σ-lone-pair orbital of E(PH 3 ) 2 and NHE Me where E=C for tetrylones and E=C, Si, Ge for tetrylenes, whereas the (CO) 5 W←E donation in the side-on bonded complexes when E becomes heavier arises from the π-lone-pair orbital of E(PH 3 ) 2 and NHE Me ligands which is the HOMO of the free ligands. This makes the heavier adducts of tetrylones and tetrylenes become stronger donors than the lighter systems. The NBO analysis suggests that the E(PH 3 ) 2 ligands are strong σ-donors and strong π-acceptors while the NHE Me ligands are strong σ-donors and weak π-acceptors. This is possible for tetrylones that have two lone-pair orbitals available for donation, whereas the tetrylenes have only one lone-pair orbital available for donation. (author)

Spectroscopic (FT-IR, FT-Raman, NMR and UV-Visible) and quantum chemical studies of molecular geometry, Frontier molecular orbital, NLO, NBO and thermodynamic properties of salicylic acid.

Science.gov (United States)

Suresh, S; Gunasekaran, S; Srinivasan, S

2014-11-11

The solid phase FT-IR and FT-Raman spectra of 2-hydroxybenzoic acid (salicylic acid) have been recorded in the region 4000-400 and 4000-100 cm(-1) respectively. The optimized molecular geometry and fundamental vibrational frequencies are interpreted with the aid of structure optimizations and normal coordinate force field calculations based on density functional theory (DFT) method and a comparative study between Hartree Fork (HF) method at 6-311++G(d,p) level basis set. The calculated harmonic vibrational frequencies are scaled and they are compared with experimentally obtained FT-IR and FT-Raman spectra. A detailed interpretation of the vibrational spectra of this compound has been made on the basis of the calculated potential energy distribution (PED). The time dependent DFT method is employed to predict its absorption energy and oscillator strength. The linear polarizability (α) and the first order hyper polarizability (β) values of the investigated molecule have been computed. The electronic properties, such as HOMO and LUMO energies, molecular electrostatic potential (MEP) are also performed. Stability of the molecule arising from hyper conjugative interaction, charge delocalization has been analyzed using natural bond orbital (NBO) analysis. Published by Elsevier B.V.

Excitation two-center interference and the orbital geometry in laser-induced nonsequential double ionization of diatomic molecules

International Nuclear Information System (INIS)

Shaaran, T.; Augstein, B. B.; Figueira de Morisson Faria, C.

2011-01-01

We address the influence of the molecular orbital geometry and of the molecular alignment with respect to the laser-field polarization on laser-induced nonsequential double ionization of diatomic molecules for different molecular species, namely N 2 and Li 2 . We focus on the recollision excitation with subsequent tunneling ionization (RESI) mechanism, in which the first electron, upon return, promotes the second electron to an excited state, from where it subsequently tunnels. We assume that both electrons are initially in the highest occupied molecular orbital (HOMO) and that the second electron is excited to the lowest unoccupied molecular orbital (LUMO). We show that the electron-momentum distributions exhibit interference maxima and minima due to the electron emission at spatially separated centers. We provide generalized analytical expressions for such maxima or minima, which take into account s-p mixing and the orbital geometry. The patterns caused by the two-center interference are sharpest for vanishing alignment angle and get washed out as this parameter increases. Apart from that, there exist features due to the geometry of the LUMO, which may be observed for a wide range of alignment angles. Such features manifest themselves as the suppression of probability density in specific momentum regions due to the shape of the LUMO wave function, or as an overall decrease in the RESI yield due to the presence of nodal planes.

Electronic properties of single-molecule junction: Effect of the molecular distortion

International Nuclear Information System (INIS)

Gao, W.; Zhao, M.; Jiang, Q.

2009-01-01

For a model system consisting of a benzenedithio (BDT) molecule sandwiched between two Au plates, the electronic properties as a function of different BDT geometry are investigated using density functional theory. The distorted BDT structures are got through stretching the electrode distance. The corresponding electronic properties, including the spatial distribution of the frontier orbits, the gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital levels and density of states at the Fermi energy are determined. It reveals that the molecular distortion essentially determines electronic structures. The result should be beneficial to understand the stress-dependent or structure-dependent transport mechanism of electrons of the BDT junction.

Bending of conjugated molecular wires and its effect on electron conduction properties

International Nuclear Information System (INIS)

Das, Bidisa

2010-01-01

The electronic structure and electron transport properties of simple conjugated molecular wires like oligophenylene ethynylene (OPE) and oligophenylene vinylene (OPV) are studied under compression. If artificially confined to a given shorter length, the oligomers tend to bend and bending causes a loss in the overlap of the conjugated molecular orbitals. Theoretical modeling of electronic transport has been carried out for all undistorted and compressed OPE/OPV oligomers. OPV exists in step-like or V-like conformations and they have the same stability with very similar frontier molecular orbitals. The conductances of these molecular wires are calculated when inserted between two gold probes and the conductances for OPV are found to be comparable to OPE when the interfaces are same. The conductance decreases with bending due to the gradual loss in overlap of the molecular orbitals. It is also found that the conductances of the molecular wires decrease very strongly if the terminal sulfur atom is simultaneously bonded to hydrogen and a gold surface, thus reflecting the importance of the interface in determining the conductance in two-probe systems. From the conductance studies it may be concluded that if one or more benzene rings of OPE are rotated from coplanar conditions, the orthogonal molecular orbitals may completely block the electronic transport, rendering the molecule insulating.

Vibrational spectra (FT-IR, FT-Raman), frontier molecular orbital, first hyperpolarizability, NBO analysis and thermodynamics properties of Piroxicam by HF and DFT methods

Science.gov (United States)

Suresh, S.; Gunasekaran, S.; Srinivasan, S.

2015-03-01

The solid phase FT-IR and FT-Raman spectra of 4-Hydroxy-2-methyl-N-(2-pyridinyl)-2H-1,2-benzothiazine-3-carboxamide-1,1-dioxide (Piroxicam) have been recorded in the region 4000-400 and 4000-100 cm-1 respectively. The molecular geometry, harmonic vibrational frequencies and bonding features of piroxicam in the ground state have been calculated by Hartree-Fock (HF) and density functional theory (DFT) methods using 6-311++G(d,p) basis set. The calculated harmonic vibrational frequencies are scaled and they are compared with experimental obtained by FT-IR and FT-Raman spectra. A detailed interpretation of the vibrational spectra of the title compound has been made on the basis of the calculated potential energy distribution (PED). The electronic properties, such as HOMO and LUMO energies, molecular electrostatic potential (MESP) are also performed. The linear polarizability (α) and the first order hyper polarizability (β) values of the title compound have been computed. The molecular stability arising from hyper conjugative interaction, charge delocalization has been analyzed using natural bond orbital (NBO) analysis.

Probing Transient Valence Orbital Changes with Picosecond Valence-to-Core X-ray Emission Spectroscopy

DEFF Research Database (Denmark)

March, Anne Marie; Assefa, Tadesse A.; Boemer, Christina

2017-01-01

We probe the dynamics of valence electrons in photoexcited [Fe(terpy)2]2+ in solution to gain deeper insight into the Fe ligand bond changes. We use hard X-ray emission spectroscopy (XES), which combines element specificity and high penetration with sensitivity to orbital structure, making...... valence orbitals to the nascent core-hole. Vtc-XES offers particular insight into the molecular orbitals directly involved in the light-driven dynamics; a change in the metal ligand orbital overlap results in an intensity reduction and a blue energy shift in agreement with our theoretical calculations...... and more subtle features at the highest energies reflect changes in the frontier orbital populations....

Accurate density functional prediction of molecular electron affinity with the scaling corrected Kohn–Sham frontier orbital energies

Science.gov (United States)

Zhang, DaDi; Yang, Xiaolong; Zheng, Xiao; Yang, Weitao

2018-04-01

Electron affinity (EA) is the energy released when an additional electron is attached to an atom or a molecule. EA is a fundamental thermochemical property, and it is closely pertinent to other important properties such as electronegativity and hardness. However, accurate prediction of EA is difficult with density functional theory methods. The somewhat large error of the calculated EAs originates mainly from the intrinsic delocalisation error associated with the approximate exchange-correlation functional. In this work, we employ a previously developed non-empirical global scaling correction approach, which explicitly imposes the Perdew-Parr-Levy-Balduz condition to the approximate functional, and achieve a substantially improved accuracy for the calculated EAs. In our approach, the EA is given by the scaling corrected Kohn-Sham lowest unoccupied molecular orbital energy of the neutral molecule, without the need to carry out the self-consistent-field calculation for the anion.

Ab initio molecular orbital and infrared spectroscopic study of the conformation of secondary amides: derivatives of formanilide, acetanilide and benzylamides

Science.gov (United States)

Ilieva, S.; Hadjieva, B.; Galabov, B.

1999-09-01

Ab initio molecular orbital calculations at HF/4-31G level and infrared spectroscopic data for the frequencies are applied to analyse the grouping in a series model aromatic secondary amides: formanilide; acetanilide; o-methylacetanilide; 2,6-dimethylformanilide, 2,6-dimethylacetanilide; N-benzylacetamide and N-benzylformamide. The theoretical and experimental data obtained show that the conformational state of the molecules studied is determined by the fine balance of several intramolecular factors: resonance effect between the amide group and the aromatic ring, steric interaction between various substituents around the -NH-CO- grouping in the aromatic ring, conjugation between the carbonyl bond and the nitrogen lone pair as well as direct field influences inside the amide group.

Calculation of photoionization differential cross sections using complex Gauss-type orbitals.

Science.gov (United States)

Matsuzaki, Rei; Yabushita, Satoshi

2017-09-05

Accurate theoretical calculation of photoelectron angular distributions for general molecules is becoming an important tool to image various chemical reactions in real time. We show in this article that not only photoionization total cross sections but also photoelectron angular distributions can be accurately calculated using complex Gauss-type orbital (cGTO) basis functions. Our method can be easily combined with existing quantum chemistry techniques including electron correlation effects, and applied to various molecules. The so-called two-potential formula is applied to represent the transition dipole moment from an initial bound state to a final continuum state in the molecular coordinate frame. The two required continuum functions, the zeroth-order final continuum state and the first-order wave function induced by the photon field, have been variationally obtained using the complex basis function method with a mixture of appropriate cGTOs and conventional real Gauss-type orbitals (GTOs) to represent the continuum orbitals as well as the remaining bound orbitals. The complex orbital exponents of the cGTOs are optimized by fitting to the outgoing Coulomb functions. The efficiency of the current method is demonstrated through the calculations of the asymmetry parameters and molecular-frame photoelectron angular distributions of H2+ and H2 . In the calculations of H2 , the static exchange and random phase approximations are employed, and the dependence of the results on the basis functions is discussed. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

An Efficient Method to Evaluate Intermolecular Interaction Energies in Large Systems Using Overlapping Multicenter ONIOM and the Fragment Molecular Orbital Method

Science.gov (United States)

Asada, Naoya; Fedorov, Dmitri G.; Kitaura, Kazuo; Nakanishi, Isao; Merz, Kenneth M.

2012-01-01

We propose an approach based on the overlapping multicenter ONIOM to evaluate intermolecular interaction energies in large systems and demonstrate its accuracy on several representative systems in the complete basis set limit at the MP2 and CCSD(T) level of theory. In the application to the intermolecular interaction energy between insulin dimer and 4′-hydroxyacetanilide at the MP2/CBS level, we use the fragment molecular orbital method for the calculation of the entire complex assigned to the lowest layer in three-layer ONIOM. The developed method is shown to be efficient and accurate in the evaluation of the protein-ligand interaction energies. PMID:23050059

Total-energy global optimizations using nonorthogonal localized orbitals

International Nuclear Information System (INIS)

Kim, J.; Mauri, F.; Galli, G.

1995-01-01

An energy functional for orbital-based O(N) calculations is proposed, which depends on a number of nonorthogonal, localized orbitals larger than the number of occupied states in the system, and on a parameter, the electronic chemical potential, determining the number of electrons. We show that the minimization of the functional with respect to overlapping localized orbitals can be performed so as to attain directly the ground-state energy, without being trapped at local minima. The present approach overcomes the multiple-minima problem present within the original formulation of orbital-based O(N) methods; it therefore makes it possible to perform O(N) calculations for an arbitrary system, without including any information about the system bonding properties in the construction of the input wave functions. Furthermore, while retaining the same computational cost as the original approach, our formulation allows one to improve the variational estimate of the ground-state energy, and the energy conservation during a molecular dynamics run. Several numerical examples for surfaces, bulk systems, and clusters are presented and discussed

QSPR Calculation of Normal Boiling Points of Organic Molecules Based on the Use of Correlation Weighting of Atomic Orbitals with Extended Connectivity of Zero- and First-Order Graphs of Atomic Orbitals

Directory of Open Access Journals (Sweden)

Eduardo A. Castro

2004-12-01

Full Text Available We report the results of a calculation of the normal boiling points of a representative set of 200 organic molecules through the application of QSPR theory. For this purpose we have used a particular set of flexible molecular descriptors, the so called Correlation Weighting of Atomic Orbitals with Extended Connectivity of Zero- and First-Order Graphs of Atomic Orbitals. Although in general the results show suitable behavior to predict this physical chemistry property, the existence of some deviant behaviors points to a need to complement this index with some other sort of molecular descriptors. Some possible extensions of this study are discussed.

Molecular and electronic structure of osmium complexes confined to Au(111) surfaces using a self-assembled molecular bridge

Energy Technology Data Exchange (ETDEWEB)

Llave, Ezequiel de la; Herrera, Santiago E.; Adam, Catherine; Méndez De Leo, Lucila P.; Calvo, Ernesto J.; Williams, Federico J., E-mail: fwilliams@qi.fcen.uba.ar [INQUIMAE-CONICET, Departamento de Química Inorgánica, Analítica y Química-Física, Facultad Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pabellón 2, Buenos Aires C1428EHA (Argentina)

2015-11-14

The molecular and electronic structure of Os(II) complexes covalently bonded to self-assembled monolayers (SAMs) on Au(111) surfaces was studied by means of polarization modulation infrared reflection absorption spectroscopy, photoelectron spectroscopies, scanning tunneling microscopy, scanning tunneling spectroscopy, and density functional theory calculations. Attachment of the Os complex to the SAM proceeds via an amide covalent bond with the SAM alkyl chain 40° tilted with respect to the surface normal and a total thickness of 26 Å. The highest occupied molecular orbital of the Os complex is mainly based on the Os(II) center located 2.2 eV below the Fermi edge and the LUMO molecular orbital is mainly based on the bipyridine ligands located 1.5 eV above the Fermi edge.

Determination of fragment orbitals and LCFO MO's in semiempirical methods with overlap matrices

International Nuclear Information System (INIS)

Konstantinavicius, K.V.; Lazauskas, V.M.

1988-01-01

We propose a technique for a fragment stage solution of the Roothaan equations, allowing us to obtain fragment orbitals (FO's) and to form molecular orbitals (LCFO MO'S) for the molecule from them. As an example, in the Mulliken-Wolfsberg-Helmholtz (MWH) approximation we obtain the orbitals for fragments of the simplest hydrocarbon molecules and we compare them with the FO's found in the CNDO/2 approximation. We discuss the possibilities in perturbation theory for joining the fragments and for study of the properties of the molecules in the FO basis

Orbital momentum distributions and binding energies for the complete valence shell of molecular iodine

International Nuclear Information System (INIS)

Grisogono, A.M.; Pascual, R.; Weigold, E.

1988-03-01

The complete valence shell binding energy spectrum (8-43eV) of I 2 has been measured by using electron momentum spectroscopy at 1000eV. The complete inner valence region, corresponding to ionization from the 10 σ u and 10 σ g orbitals, has been measured for the first time and shows extensive splitting of the ionization strength due to electron correlation effects in the ion. Many-body calculations using the Green's function method have been carried out and are compared with the data. Momentum distributions, measured in both the outer and inner valence regions, are compared with those given by SCF orbital wave functions calculated with a number of different basis sets. Computed orbital position and momentum density maps for oriented I 2 molecules are discussed in comparison with the measured and calculated spherically averaged momentum distributions

Self-consistent coupling of atomic orbitals to a moving charge

International Nuclear Information System (INIS)

Da Costa, H.F.M.; Micha, D.A.

1994-01-01

The authors describe the time evolution of hydrogenic orbitals perturbed by a moving charge. Starting with the equation for an atom interacting with a charge, the authors use an eikonal representation of the total wave-function, followed by an eikonal approximation, to derive coupled differential equations for the temporal change of the orbitals and the charge's trajectory. The orbitals are represented by functions with complex exponents changing with time, describing electronic density and flux changes. For each orbital, they solve a set of six coupled differential equations; two of them are derived with a time-dependent variational procedure for the real and imaginary parts of the exponents, and the other four are the Hamilton equations of the positions and momenta of the moving charge. The molecular potentials are derived from the exact expressions for the electronic energies. Results of calculations for 1s and 2s orbitals show large variation of the real exponent parts over time, with respect to asymptotic values, and that imaginary parts remain small

Machine Learning Methods to Predict Density Functional Theory B3LYP Energies of HOMO and LUMO Orbitals.

Science.gov (United States)

Pereira, Florbela; Xiao, Kaixia; Latino, Diogo A R S; Wu, Chengcheng; Zhang, Qingyou; Aires-de-Sousa, Joao

2017-01-23

Machine learning algorithms were explored for the fast estimation of HOMO and LUMO orbital energies calculated by DFT B3LYP, on the basis of molecular descriptors exclusively based on connectivity. The whole project involved the retrieval and generation of molecular structures, quantum chemical calculations for a database with >111 000 structures, development of new molecular descriptors, and training/validation of machine learning models. Several machine learning algorithms were screened, and an applicability domain was defined based on Euclidean distances to the training set. Random forest models predicted an external test set of 9989 compounds achieving mean absolute error (MAE) up to 0.15 and 0.16 eV for the HOMO and LUMO orbitals, respectively. The impact of the quantum chemical calculation protocol was assessed with a subset of compounds. Inclusion of the orbital energy calculated by PM7 as an additional descriptor significantly improved the quality of estimations (reducing the MAE in >30%).

Spin-orbit-induced spin splittings in polar transition metal dichalcogenide monolayers

KAUST Repository

Cheng, Yingchun; Zhu, Zhiyong; Tahir, Muhammad; Schwingenschlö gl, Udo

2013-01-01

. We present ab initio electronic structure, phonon, and molecular-dynamics calculations to study the structural stability and spin-orbit-induced spin splitting in the transition metal dichalcogenide monolayers MXY (M = Mo, W and X, Y = S, Se, Te

Induced Orbital Paramagnetism and Paratropism in Closed-Shell Molecules

Science.gov (United States)

Pelloni, Stefano; Lazzeretti, Paolo; Zanasi, Riccardo

2009-07-01

Three-dimensional models of the quantum-mechanical current density induced by a uniform magnetic field in the electron cloud have been obtained for closed-shell systems BeH-, BH, and CH+, characterized by induced orbital paramagnetism, and in planar unsaturated hydrocarbons C4H4 and clamped C8H8, exhibiting π paramagnetism. It is shown that, even for these paramagnetic systems, the paramagnetic contributions to magnetic susceptibilities and nuclear magnetic shielding, customarily taken into account in perturbation theory approaches, can formally be eliminated via the procedure of continuous transformation of the origin of the current density-paramagnetic zero. The definition of magnetic response properties can therefore be recast as a sum of two formally "diamagnetic" terms for any molecule, including systems showing strong induced orbital paramagnetism. It is shown that the paramagnetism in the compounds studied arises from the nodal topology of the electronic wave function. In particular, paratropic vortices circulate about stagnation lines at the intersection of nodal surfaces of the highest-occupied zero-order molecular orbital and corresponding first-order orbital.

First-principles molecular dynamics study of Al/Alq3 interfaces

Directory of Open Access Journals (Sweden)

Kousuke Takeuchi et al

2007-01-01

Full Text Available We have carried out first-principles molecular dynamics simulations of Al deposition on tris (8-hydroxyquinoline aluminum (Alq3 layers to investigate atomic geometries and electronic properties of Al/Alq3 interfaces. Al atoms were ejected to Alq3 one by one with the kinetic energy of 37.4 kJ/mol, which approximately corresponds to the average kinetic energy of Al at the boiling temperature of metal Al. The first Al atom interacts with two of the three O atoms of meridional Alq3. Following Al atoms interact with Alq3 rather weakly and they tend to aggregate each other to form Al clusters. During the deposition process, Alq3 was not broken and its molecular structure remained essentially intact. At the interface, weak bonds between deposited Al atoms and N and C atoms were formed. The projected density of states (PDOS onto the Alq3 molecular orbitals shows gap states in between the highest occupied molecular orbitals (HOMOs and the lowest unoccupied molecular orbitals (LUMOs, which were experimentally observed by ultraviolet photoelectron spectroscopy (UPS and metastable atom electron spectroscopy (MAES. Our results show that even though the Alq3 molecular structure is retained, weak N–Al and C–Al bonds induce gap states.

Mean Orbital Elements for Geosynchronous Orbit - II - Orbital inclination, longitude of ascending node, mean longitude

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Kyu-Hong Choi

1990-06-01

Full Text Available The osculating orbital elements include the mean, secular, long period, and short period terms. The iterative algorithm used for conversion of osculating orbital elements to mean orbital elements is described. The mean orbital elements of Wc, Ws, and L are obtained.

[Orbital inflammation].

Science.gov (United States)

Mouriaux, F; Coffin-Pichonnet, S; Robert, P-Y; Abad, S; Martin-Silva, N

2014-12-01

Orbital inflammation is a generic term encompassing inflammatory pathologies affecting all structures within the orbit : anterior (involvement up to the posterior aspect of the globe), diffuse (involvement of intra- and/or extraconal fat), apical (involvement of the posterior orbit), myositis (involvement of only the extraocular muscles), dacryoadenitis (involvement of the lacrimal gland). We distinguish between specific inflammation and non-specific inflammation, commonly referred to as idiopathic inflammation. Specific orbital inflammation corresponds to a secondary localization of a "generalized" disease (systemic or auto-immune). Idiopathic orbital inflammation corresponds to uniquely orbital inflammation without generalized disease, and thus an unknown etiology. At the top of the differential diagnosis for specific or idiopathic orbital inflammation are malignant tumors, represented most commonly in the adult by lympho-proliferative syndromes and metastases. Treatment of specific orbital inflammation begins with treatment of the underlying disease. For idiopathic orbital inflammation, treatment (most often corticosteroids) is indicated above all in cases of visual loss due to optic neuropathy, in the presence of pain or oculomotor palsy. Copyright © 2014 Elsevier Masson SAS. All rights reserved.

PyORBIT: A Python Shell For ORBIT

Energy Technology Data Exchange (ETDEWEB)

Jean-Francois Ostiguy; Jeffrey Holmes

2003-07-01

ORBIT is code developed at SNS to simulate beam dynamics in accumulation rings and synchrotrons. The code is structured as a collection of external C++ modules for SuperCode, a high level interpreter shell developed at LLNL in the early 1990s. SuperCode is no longer actively supported and there has for some time been interest in replacing it by a modern scripting language, while preserving the feel of the original ORBIT program. In this paper, we describe a new version of ORBIT where the role of SuperCode is assumed by Python, a free, well-documented and widely supported object-oriented scripting language. We also compare PyORBIT to ORBIT from the standpoint of features, performance and future expandability.

PyORBIT: A Python Shell For ORBIT

International Nuclear Information System (INIS)

Jean-Francois Ostiguy; Jeffrey Holmes

2003-01-01

ORBIT is code developed at SNS to simulate beam dynamics in accumulation rings and synchrotrons. The code is structured as a collection of external C++ modules for SuperCode, a high level interpreter shell developed at LLNL in the early 1990s. SuperCode is no longer actively supported and there has for some time been interest in replacing it by a modern scripting language, while preserving the feel of the original ORBIT program. In this paper, we describe a new version of ORBIT where the role of SuperCode is assumed by Python, a free, well-documented and widely supported object-oriented scripting language. We also compare PyORBIT to ORBIT from the standpoint of features, performance and future expandability

The analytic gradient with a reduced molecular orbital space for the equation-of-motion coupled-cluster theory: systematic study of the magnitudes and trends in simple molecules

International Nuclear Information System (INIS)

Baeck, Kyoung K.; Jeon, Sang Il

2000-01-01

The analytic gradient method for the equation-of-motion coupled-cluster singles and doubles (EOM-CCSD) energy has been extended to employ a reduced molecular orbital (MO) space. Not only the innermost core MO s but also some of the outermost virtual MO s can be dropped in the reduced MO space, and a substantial amount of computation time can be reduced without deteriorating the results. In order to study the magnitudes and trends of the effects of the dropped MO s , the geometries and vibrational properties of the ground and excited states of BF, CO, CN, N 2 , AlCl, SiS, P 2 , BCl, AlF, CS, SiO, PN and GeSe are calculated with different sizes of molecular orbital space. The 6-31G and the aug-cc-pVTZ basis sets are employed for all molecules except GeSe for which the 6-311 G and the TZV+f basis sets are used. It is shown that the magnitudes of the drop MO effects are about 0.005 A in bond lengths and about 1% on harmonic frequencies and IR intensities provided that the dropped MO s correspond to (1s), (1s,2s,2p), and (1s,2s,2p,3s,3p) atomic orbitals of the first, the second, and the third row atoms, respectively. The geometries and vibrational properties of the first and the second excited states of HCN and HCN are calculated by using a drastically reduced virtual MO space as well as with the well defined frozen core MO space. The results suggest the possibility of using a very small MO space for qualitative study of valence excited states

Vibrational spectra, molecular structure, natural bond orbital, first order hyperpolarizability, thermodynamic analysis and normal coordinate analysis of Salicylaldehyde p-methylphenylthiosemicarbazone by density functional method

Science.gov (United States)

Porchelvi, E. Elamurugu; Muthu, S.

2015-01-01

The thiosemicarbazone compound, Salicylaldehyde p-methylphenylthiosemicarbazone (abbreviated as SMPTSC) was synthesized and characterized by FTIR, FT-Raman and UV. Density functional (DFT) calculations have been carried out for the title compound by performing DFT level of theory using B3LYP/6-31++G(d,p) basis set. The molecular geometry and vibrational frequencies were calculated and compared with the experimental data. The detailed interpretation of the vibrational spectra has been carried out with aid of normal coordinate analysis (NCA) following the scaled quantum mechanical force field methodology. The electronic dipole moment (μD) and the first hyperpolarizability (βtot) values of the investigated molecule were computed using density functional theory (DFT/B3LYP) with 6-311++G(d,p) basis set. The stability and charge delocalization of the molecule was studied by natural bond orbital (NBO) analysis. Thearomaticities of the phenyl rings were studied using the standard harmonic oscillator model of aromaticity (HOMA) index. Mulliken population analysis on atomic charges is also calculated. The molecule orbital contributions are studied by density of energy states (DOSs).

X-ray photoelectron spectra structure of actinide compounds stipulated by electrons of the inner valence molecular orbitals (IVMO)

International Nuclear Information System (INIS)

Teterin, Yu. A.; Ivanov, K. E.

1997-01-01

Development of precise X-ray photoelectron spectroscopy using X-ray radiation hν< 1.5 KeV allowed to carry out immediate investigations of fine spectra structure of both weakly bond and deep electrons. Based on the experiments and the obtained results it may be concluded: 1. Under favourable conditions the inner valence molecular orbitals (IVMO) may form in all actinide compounds. 2. The XPS spectra fine structure stipulated by IVMO electrons allows to judge upon the degree of participation of the filled AO electrons in the chemical bond, on the structure o considered atom close environment and the bond lengths in compounds. For amorphous compounds the obtaining of such data based on X-ray structure analysis is restricted. 3. The summary contribution of IVMO electrons to the absolute value of the chemical bonding is comparable with the corresponding value of OMO electrons contribution to the atomic bonding. This fact is very important and new in chemistry. (author)

Discontinuous approximate molecular electronic wave-functions

International Nuclear Information System (INIS)

Stuebing, E.W.; Weare, J.H.; Parr, R.G.

1977-01-01

Following Kohn, Schlosser and Marcus and Weare and Parr an energy functional is defined for a molecular problem which is stationary in the neighborhood of the exact solution and permits the use of trial functions that are discontinuous. The functional differs from the functional of the standard Rayleigh--Ritz method in the replacement of the usual kinetic energy operators circumflex T(μ) with operators circumflex T'(μ) = circumflex T(μ) + circumflex I(μ) generates contributions from surfaces of nonsmooth behavior. If one uses the nabla PSI . nabla PSI way of writing the usual kinetic energy contributions, one must add surface integrals of the product of the average of nabla PSI and the change of PSI across surfaces of discontinuity. Various calculations are carried out for the hydrogen molecule-ion and the hydrogen molecule. It is shown that ab initio calculations on molecules can be carried out quite generally with a basis of atomic orbitals exactly obeying the zero-differential overlap (ZDO) condition, and a firm basis is thereby provided for theories of molecular electronic structure invoking the ZDO aoproximation. It is demonstrated that a valence bond theory employing orbitals exactly obeying ZDO can provide an adequate account of chemical bonding, and several suggestions are made regarding molecular orbital methods

Synthesis, spectroscopic investigations, DFT studies, molecular docking and antimicrobial potential of certain new indole-isatin molecular hybrids: Experimental and theoretical approaches

Science.gov (United States)

Almutairi, Maha S.; Zakaria, Azza S.; Ignasius, P. Primsa; Al-Wabli, Reem I.; Joe, Isaac Hubert; Attia, Mohamed I.

2018-02-01

Indole-isatin molecular hybrids 5a-i have been synthesized and characterized by different spectroscopic methods to be evaluated as new antimicrobial agents against a panel of Gram positive bacteria, Gram negative bacteria, and moulds. Compound 5h was selected as a representative example of the prepared compounds 5a-i to perform computational investigations. Its vibrational properties have been studied using FT-IR and FT-Raman with the aid of density functional theory approach. The natural bond orbital analysis as well as HOMO and LUMO molecular orbitals investigations of compound 5h were carried out to explore its possible intermolecular delocalization or hyperconjugation and its possible interactions with the target protein. Molecular docking of compound 5h predicted its binding mode with the fungal target protein.

Orbit Propagation and Determination of Low Earth Orbit Satellites

Directory of Open Access Journals (Sweden)

Ho-Nien Shou

2014-01-01

Full Text Available This paper represents orbit propagation and determination of low Earth orbit (LEO satellites. Satellite global positioning system (GPS configured receiver provides position and velocity measures by navigating filter to get the coordinates of the orbit propagation (OP. The main contradictions in real-time orbit which is determined by the problem are orbit positioning accuracy and the amount of calculating two indicators. This paper is dedicated to solving the problem of tradeoffs. To plan to use a nonlinear filtering method for immediate orbit tasks requires more precise satellite orbit state parameters in a short time. Although the traditional extended Kalman filter (EKF method is widely used, its linear approximation of the drawbacks in dealing with nonlinear problems was especially evident, without compromising Kalman filter (unscented Kalman Filter, UKF. As a new nonlinear estimation method, it is measured at the estimated measurements on more and more applications. This paper will be the first study on UKF microsatellites in LEO orbit in real time, trying to explore the real-time precision orbit determination techniques. Through the preliminary simulation results, they show that, based on orbit mission requirements and conditions using UKF, they can satisfy the positioning accuracy and compute two indicators.

Rehabilitation of orbital cavity after orbital exenteration using polymethyl methacrylate orbital prosthesis

Directory of Open Access Journals (Sweden)

Sumeet Jain

2016-01-01

Full Text Available Squamous cell carcinoma of the eyelid is the second most common malignant neoplasm of the eye with the incidence of 0.09 and 2.42 cases/100 000 people. Orbital invasion is a rare complication but, if recognized early, can be treated effectively with exenteration. Although with advancements in technology such as computer-aided design and computer-aided manufacturing, material science, and retentive methods like implants, orbital prosthesis with stock ocular prosthesis made of methyl methacrylate retained by anatomic undercuts is quiet effective and should not be overlooked and forgotten. This clinical report describes prosthetic rehabilitation of two male patients with polymethyl methacrylate resin orbital prosthesis after orbital exenteration, for squamous cell carcinoma of the upper eyelid. The orbital prosthesis was sufficiently retained by hard and soft tissue undercuts without any complications. The patients using the prosthesis are quite satisfied with the cosmetic results and felt comfortable attending the social events.

ORBITAL INJURIES

Directory of Open Access Journals (Sweden)

Andrej Kansky

2002-12-01

Full Text Available Background. Orbit is involved in 40% of all facial fractures. There is considerable variety in severity, ranging from simple nondisplaced to complex comminuted fractures. Complex comminuted fractures (up to 20% are responsible for the majority of complications and unfavorable results. Orbital fractures are classified as internal orbital fractures, zygomatico-orbital fractures, naso-orbito-ethmoidal fractures and combined fractures. The ophtalmic sequelae of midfacial fractures are usually edema and ecchymosis of the soft tissues, subconjuctival hemorrhage, diplopia, iritis, retinal edema, ptosis, enophthalmos, ocular muscle paresis, mechanical restriction of ocular movement and nasolacrimal disturbances. More severe injuries such as optic nerve trauma and retinal detachments have also been reported. Within the wide range of orbital fractures small group of complex fractures causes most of the sequelae. Therefore identification of severe injuries and adequate treatment is of major importance. The introduction of craniofacial techniques made possible a wide exposure even of large orbital wall defects and their reconstruction by bone grafts. In spite of significant progress, repair of complex orbital wall defects remains a problem even for the experienced surgeons.Results. In 1999 121 facial injuries were treated at our department (Clinical Centre Ljubljana Dept. Of Maxillofacial and Oral Surgery. Orbit was involved in 65% of cases. Isolated inner orbital fractures presented 4% of all fractures. 17 (14% complex cases were treated, 5 of them being NOE, 5 orbital (frame and inner walls, 3 zygomatico-orbital, 2 FNO and 2 maxillo-orbital fractures.Conclusions. Final result of the surgical treatment depends on severity of maxillofacial trauma. Complex comminuted fractures are responsable for most of the unfavorable results and ocular function is often permanently damaged (up to 75% in these fractures.

Molecular orbital (SCF-Xα-SW) theory of metal-metal charge transfer processes in minerals - II. Application to Fe2+ --> Ti4+ charge transfer transitions in oxides and silicates

Science.gov (United States)

Sherman, David M.

1987-01-01

A molecular orbital description, based on Xα-Scattered wave calculations on a (FeTiO10)14− cluster, is given for Fe2+ → Ti4+ charge transfer transitions in minerals. The calculated energy for the lowest Fe2+ → Ti4+ metal-metal charge transfer transition is 18040 cm−1 in reasonable agreement with energies observed in the optical spectra of Fe-Ti oxides and silicates. As in the case of Fe2+ → Fe3+ charge transfer in mixed-valence iron oxides and silicates, Fe2+ → Ti4+ charge transfer is associated with Fe-Ti bonding across shared polyhedral edges. Such bonding results from the overlap of the Fe(t 2g ) and Ti(t 2g ) 3d orbitals.

Orbital

OpenAIRE

Yourshaw, Matthew Stephen

2017-01-01

Orbital is a virtual reality gaming experience designed to explore the use of traditional narrative structure to enhance immersion in virtual reality. The story structure of Orbital was developed based on the developmental steps of 'The Hero's Journey,' a narrative pattern identified by Joseph Campbell. Using this standard narrative pattern, Orbital is capable of immersing the player quickly and completely for the entirety of play time. MFA

Theory and practice of uncommon molecular electronic configurations.

Science.gov (United States)

Gryn'ova, Ganna; Coote, Michelle L; Corminboeuf, Clemence

2015-01-01

The electronic configuration of the molecule is the foundation of its structure and reactivity. The spin state is one of the key characteristics arising from the ordering of electrons within the molecule's set of orbitals. Organic molecules that have open-shell ground states and interesting physicochemical properties, particularly those influencing their spin alignment, are of immense interest within the up-and-coming field of molecular electronics. In this advanced review, we scrutinize various qualitative rules of orbital occupation and spin alignment, viz., the aufbau principle, Hund's multiplicity rule, and dynamic spin polarization concept, through the prism of quantum mechanics. While such rules hold in selected simple cases, in general the spin state of a system depends on a combination of electronic factors that include Coulomb and Pauli repulsion, nuclear attraction, kinetic energy, orbital relaxation, and static correlation. A number of fascinating chemical systems with spin states that fluctuate between triplet and open-shell singlet, and are responsive to irradiation, pH, and other external stimuli, are highlighted. In addition, we outline a range of organic molecules with intriguing non-aufbau orbital configurations. In such quasi-closed-shell systems, the singly occupied molecular orbital (SOMO) is energetically lower than one or more doubly occupied orbitals. As a result, the SOMO is not affected by electron attachment to or removal from the molecule, and the products of such redox processes are polyradicals. These peculiar species possess attractive conductive and magnetic properties, and a number of them that have already been developed into molecular electronics applications are highlighted in this review. WIREs Comput Mol Sci 2015, 5:440-459. doi: 10.1002/wcms.1233 For further resources related to this article, please visit the WIREs website.

Low temperature FT-IR and molecular orbital study of N,N-dimethylglycine methyl ester: Proof for different ground conformational states in gas phase and in condensed media

OpenAIRE

Gómez-Zavaglia, A.; Fausto, R.

2002-01-01

N,N-dimethylglycine methyl ester (DMG-Me) was studied by FT-IR spectroscopy under several experimental conditions, including low temperature solid state and isolated in low temperature inert gas matrices, and by molecular orbital calculations. In agreement with the theoretical predictions, the experimental data show that in the gaseous phase the most stable conformer (ASC) has the ester group in cis configuration and the N–C–CO and Lp–N–C–C (Lp=lone electron pair) dihedral angles equal to 0° ...

Orbit Functions

Directory of Open Access Journals (Sweden)

Anatoliy Klimyk

2006-01-01

Full Text Available In the paper, properties of orbit functions are reviewed and further developed. Orbit functions on the Euclidean space E_n are symmetrized exponential functions. The symmetrization is fulfilled by a Weyl group corresponding to a Coxeter-Dynkin diagram. Properties of such functions will be described. An orbit function is the contribution to an irreducible character of a compact semisimple Lie group G of rank n from one of its Weyl group orbits. It is shown that values of orbit functions are repeated on copies of the fundamental domain F of the affine Weyl group (determined by the initial Weyl group in the entire Euclidean space E_n. Orbit functions are solutions of the corresponding Laplace equation in E_n, satisfying the Neumann condition on the boundary of F. Orbit functions determine a symmetrized Fourier transform and a transform on a finite set of points.

Theoretical study of molecular vibrations in electron momentum spectroscopy experiments on furan: An analytical versus a molecular dynamical approach

International Nuclear Information System (INIS)

Morini, Filippo; Deleuze, Michael S.; Watanabe, Noboru; Takahashi, Masahiko

2015-01-01

The influence of thermally induced nuclear dynamics (molecular vibrations) in the initial electronic ground state on the valence orbital momentum profiles of furan has been theoretically investigated using two different approaches. The first of these approaches employs the principles of Born-Oppenheimer molecular dynamics, whereas the so-called harmonic analytical quantum mechanical approach resorts to an analytical decomposition of contributions arising from quantized harmonic vibrational eigenstates. In spite of their intrinsic differences, the two approaches enable consistent insights into the electron momentum distributions inferred from new measurements employing electron momentum spectroscopy and an electron impact energy of 1.2 keV. Both approaches point out in particular an appreciable influence of a few specific molecular vibrations of A 1 symmetry on the 9a 1 momentum profile, which can be unravelled from considerations on the symmetry characteristics of orbitals and their energy spacing

Influence of electron correlation and degeneracy on the Fukui matrix and extension of frontier molecular orbital theory to correlated quantum chemical methods.

Science.gov (United States)

Bultinck, Patrick; Van Neck, Dimitri; Acke, Guillaume; Ayers, Paul W

2012-02-21

The Fukui function is considered as the diagonal element of the Fukui matrix in position space, where the Fukui matrix is the derivative of the one particle density matrix (1DM) with respect to the number of electrons. Diagonalization of the Fukui matrix, expressed in an orthogonal orbital basis, explains why regions in space with negative Fukui functions exist. Using a test set of molecules, electron correlation is found to have a remarkable effect on the eigenvalues of the Fukui matrix. The Fukui matrices at the independent electron model level are mathematically proven to always have an eigenvalue equal to exactly unity while the rest of the eigenvalues possibly differ from zero but sum to zero. The loss of idempotency of the 1DM at correlated levels of theory causes the loss of these properties. The influence of electron correlation is examined in detail and the frontier molecular orbital concept is extended to correlated levels of theory by defining it as the eigenvector of the Fukui matrix with the largest eigenvalue. The effect of degeneracy on the Fukui matrix is examined in detail, revealing that this is another way by which the unity eigenvalue and perfect pairing of eigenvalues can disappear.

Molecular design of new hydrazone dyes for dye-sensitized solar cells: Synthesis, characterization and DFT study

KAUST Repository

Al-Sehemi, Abdullah G.

2012-07-01

Three new sensitizers 2-{4-[2-(4-Nitrobenzylidene)hydrazino)]phenyl} ethylene-1,1,2-tricarbonitrile (NBHPET), 2-{4-[2-p-Chlorobenzylidenehydrazino] phenyl}- ethylene-1,1,2-tri carbonitrile (CBHPET) and 2-{4-[2-p- Bromobenzylidenehydrazino] phenyl}ethylene-1,1,2-tricarbonitrile (BBHPET) have been synthesized. The dyes showed pronounced solvatochromic effects as the polarity of the solvents increased. The structures have been optimized at B3LYP/6-31G(d) level of theory. The torsion in E-isomer is smaller than Z-isomer and azo isomers. The highest occupied molecular orbitals are delocalized on whole molecule while lowest unoccupied molecular orbitals are distributed on the tricarbonitrile. The lowest unoccupied molecular orbital energies are above the conduction band of titanium dioxide, highest occupied molecular orbitals of the dyes are below the redox couple of new synthesized dyes and small energy gap revealed these dyes would be better sensitizers for dye-sensitized solar cells. © 2012 Elsevier B.V. All rights reserved.

Investigation of the spectroscopy and relaxation dynamics of benzaldehyde using molecular orbital calculations and laser ionization time-of-flight mass spectroscopy

Science.gov (United States)

da Silva, Maria Cristina Rodrigues

1998-11-01

Molecular orbital methods and laser ionization mass spectrometry measurements are used to investigate the spectroscopy and relaxation dynamics of benzaldehyde following excitation to its S2(/pi/pi/sp/*) state. Energies, equilibrium geometries and vibrational frequencies of ground and low-lying excited states of benzaldehyde neutral and cation determined by ab initio calculations provide a theoretical description of the electronic spectroscopy of benzaldehyde and of the changes occurring on excitation and ionization. The S2(/pi/pi/sp/*)[/gets]S0 excitation spectrum of jet-cooled benzaldehyde acquired using two-color laser ionization mass spectrometry techniques is interpreted with the aid of these calculations. The spectrum is dominated by the origin band and by transitions involving some of the ring modes consistent with the results of the molecular orbital calculations that indicate that the major geometric changes on excitation to S2 are located in the aromatic ring. Ten fundamental vibrations of the S2(/pi/pi/sp/*) state are assigned. The dissociation dynamics of benzaldehyde into benzene and carbon monoxide following excitation to its S2(/pi/pi/sp/*) state are investigated under jet- cooled conditions by two-color laser ionization mass spectrometry using a pump-probe technique. This experimental arrangement allows monitoring the benzaldehyde reactant and the benzene product ion signals as a function of the time delay between the excitation and ionization steps. A kinetic model is proposed to explain the observed biexponential decay of the benzaldehyde signal and the single exponential growth of the benzene product signal in terms of a sequential decay of two excited states of benzaldehyde, one of which leads to formation of benzene molecules in its lowest triplet state. Reactant disappearance and product appearance rates are determined for a number of vibronic transitions of the S2 state. They are found to increase with excitation energy without any indication

On the physical nature and chemical utility of Kohn-Sham orbitals

International Nuclear Information System (INIS)

Baerends, E.J.

1996-01-01

Density functional calculations almost invariably use the one-electron Kohn-Sham orbitals to calculate the electron density. It is sometimes stated that these KS orbitals have no special physical meaning, but are constructs, arising in the KS formulation of DFT, that are only useful to obtain the density. We will argue that on the contrary the KS orbitals are often very similar to the molecular orbitals that arise in the Hartree-Fock model. When they differ the Kohn-Sham orbitals have certain advantageous properties and correspond in fact more closely to the orbitals used explicitly or implicitly in qualitative MO theory. The arguments of QMO theory, with their emphasis on bonding and antibonding nature of MOs, do hold perfectly for KS orbitals. The reason that Kohn-Sham orbitals are meaningful objects is related to the fact that the effective one-electron Kohn-Sham potential embodies the effects of electron correlation. It has recently become possible to calculate accurate Kohn-Sham potentials from accurate electron densities. This offers the possibility to study the structure of KS potentials (steps, peaks) and to relate this structure to electron correlation. More importantly, given exact Kohn-Sham potentials and orbitals it is possible to construct an exchange-correlation energy density that will, after integration over space, yield the exact exchange-correlation energy. It is possible to relate the local features of the exact energy density to aspects of electron correlation. The exact energy density may be used to judge existing model exchange-correlation energy densities and hopefully it will be helpful to devise improvements

A comprehensive analysis of molecule-intrinsic quasi-atomic, bonding, and correlating orbitals. I. Hartree-Fock wave functions

International Nuclear Information System (INIS)

West, Aaron C.; Schmidt, Michael W.; Gordon, Mark S.; Ruedenberg, Klaus

2013-01-01

Through a basis-set-independent web of localizing orbital-transformations, the electronic wave function of a molecule is expressed in terms of a set of orbitals that reveal the atomic structure and the bonding pattern of a molecule. The analysis is based on resolving the valence orbital space in terms of an internal space, which has minimal basis set dimensions, and an external space. In the internal space, oriented quasi-atomic orbitals and split-localized molecular orbitals are determined by new, fast localization methods. The density matrix between the oriented quasi-atomic orbitals as well as the locations of the split-localized orbitals exhibit atomic populations and inter-atomic bonding patterns. A correlation-adapted quasi-atomic basis is determined in the external orbital space. The general formulations are specified in detail for Hartree-Fock wave functions. Applications to specific molecules exemplify the general scheme

Leakage and sweet spots in triple-quantum-dot spin qubits: A molecular-orbital study

Science.gov (United States)

Zhang, Chengxian; Yang, Xu-Chen; Wang, Xin

2018-04-01

A triple-quantum-dot system can be operated as either an exchange-only qubit or a resonant-exchange qubit. While it is generally believed that the decisive advantage of the resonant-exchange qubit is the suppression of charge noise because it is operated at a sweet spot, we show that the leakage is also an important factor. Through molecular-orbital-theoretic calculations, we show that when the system is operated in the exchange-only scheme, the leakage to states with double electron occupancy in quantum dots is severe when rotations around the axis 120∘ from z ̂ is performed. While this leakage can be reduced by either shrinking the dots or separating them further, the exchange interactions are also suppressed at the same time, making the gate operations unfavorably slow. When the system is operated as a resonant-exchange qubit, the leakage is three to five orders of magnitude smaller. We have also calculated the optimal detuning point which minimizes the leakage for the resonant-exchange qubit, and have found that although it does not coincide with the double sweet spot for the charge noise, they are rather close. Our results suggest that the resonant-exchange qubit has another advantage, that leakage can be greatly suppressed compared to the exchange-only qubit, and operating at the double sweet spot point should be optimal both for reducing charge noise and suppressing leakage.

MC SCF molecular gradients and hessians: computational aspects

Energy Technology Data Exchange (ETDEWEB)

Banerjee, A; Jensen, J O; Simons, J; Shepard, R

1984-01-01

Molecular gradients and hessians for multiconfigurational self-consistent-field wavefunctions are derived in terms of the generators of the unitary group using exponential unitary operators to describe the response of the energy to a geometrical deformation. Final expressions are cast in forms which contain reference only to the primitive non-orthogonal atomic basis set and to the final orthonormal molecular orbitals; all reference to intermediate orthogonalized orbitals is removed. All of the deformation-dependent terms in the working equations reside in the one- and two-electron integral derivatives involving the atomic basis orbitals. The deformation-independent terms, whose contributions can be partially summed, involve symmetrized density matrix elements which have the same eight-fold index permutational symmetry as the one- and two-electron integral derivatives they multiply. This separation of deformation-dependent and -independent factors allows for single-pass integral-derivative-driven implementation of the gradient and hessian expressions. 19 references.

Electronic properties of organic monolayers and molecular devices

Indian Academy of Sciences (India)

These devices exhibit a marked current–voltage rectification behavior due to resonant transport between the Si conduction band and the molecule highest occupied molecular orbital of the molecule. We discuss the role of metal Fermi level pinning in the current–voltage behavior of these molecular junctions. We also ...

ERS orbit control

Science.gov (United States)

Rosengren, Mats

1991-12-01

The European remote sensing mission orbit control is addressed. For the commissioning phase, the orbit is defined by the following requirements: Sun synchronous, local time of descending node 10:30; three days repeat cycle with 43 orbital revolutions; overhead Venice tower (12.508206 deg east, 45.314222 deg north). The launch, maneuvers for the initial acquisition of the operational orbit, orbit maintenance maneuvers, evaluation of the orbit control, and the drift of the inclination are summarized.

A Typical Presentation of Orbital Pseudotumor Mimicking Orbital Cellulitis

Directory of Open Access Journals (Sweden)

J. Ayatollahi

2013-10-01

Full Text Available Introduction: Orbital pseudotumor, also known as idiopathic orbital inflammatory syndrome (IOIS, is a benign, non- infective inflammatory condition of the orbit without identifiable local or systemic causes. The disease may mimics a variety of pathologic conditions. We pre-sent a case of pseudotumor observed in a patient admitted under the name of orbital celluli-ties. Case Report: A 26-year-old woman reffered to our hospital with the history of left ocular pain and headache 2 days before her visit.. Ophthalmological examination of the patient was normal except for the redness and lid edema, mild chemosis and conjunctival injection. Gen-eral assessment was normal but a low grade fever was observed. She was hospitalized as an orbital cellulitis patient. She was treated with intravenous antibiotics. On the third day , sud-denly diplopia, proptosis in her left eye and ocular pain in her right side appeared. MRI re-vealed bilateral enlargement of extraocular muscles. Diagnosis of orbital pseudotumor was made and the patient was treated with oral steroid.She responded promptly to the treatment. Antibiotics were discontinued and steroid was tapered in one month period under close fol-low up. Conclusion: The clinical features of orbital pseudotumor vary widely . Orbital pseudotumor and orbital cellulitis can occasionally demonstrate overlapping features.. Despite complete physical examination and appropriate imaging, sometimes correct diagnosis of the disease would be difficult (Sci J Hamadan Univ Med Sci 2013; 20 (3:256-259

Internuclear Separation Dependent Ionization of the Valence Orbitals of I2 by Strong Laser Fields

Science.gov (United States)

Chen, H.; Tagliamonti, V.; Gibson, G. N.

2012-11-01

Using a pump-dump-probe technique and Fourier-transform spectroscopy, we study the internuclear separation R dependence and relative strength of the ionization rates of the π and σ electrons of I2, whose valence orbitals are σg2πu4πg4σu0. We find that ionization of the highest occupied molecular orbital (HOMO)-2 (σg) has a strong dependence on R while the HOMO and HOMO-1 do not. Surprisingly, the ionization rate of the HOMO-2 exceeds the combined ionization rate of the less bound orbitals and this branching ratio increases with R. Since our technique produces target molecules that are highly aligned with the laser polarization, the σ orbitals will be preferentially ionized and undergo enhanced ionization at larger R compared to the π orbitals. Nevertheless, it is highly unusual that an inner orbital provides the dominant strong field ionization pathway in a small molecule.

Deadly Sunflower Orbits

Science.gov (United States)

Hamilton, Douglas P.

2018-04-01

Solar radiation pressure is usually very effective at removing hazardous millimeter-sized debris from distant orbits around asteroidsand other small solar system bodies (Hamilton and Burns 1992). Theprimary loss mechanism, driven by the azimuthal component of radiationpressure, is eccentricity growth followed by a forced collision withthe central body. One large class of orbits, however, neatly sidestepsthis fate. Orbits oriented nearly perpendicular to the solar directioncan maintain their face-on geometry, oscillating slowly around a stableequilibrium orbit. These orbits, designated sunflower orbits, arerelated to terminator orbits studied by spacecraft mission designers(Broschart etal. 2014).Destabilization of sunflower orbits occurs only for particles smallenough that radiation pressure is some tens of percent the strength ofthe central body's direct gravity. This greatly enhanced stability,which follows from the inability of radiation incident normal to theorbit to efficiently drive eccentricities, presents a threat tospacecraft missions, as numerous dangerous projectiles are potentiallyretained in orbit. We have investigated sunflower orbits insupport of the New Horizons, Aida, and Lucy missions and find thatthese orbits are stable for hazardous particle sizes at asteroids,comets, and Kuiper belt objects of differing dimensions. Weinvestigate the sources and sinks for debris that might populate suchorbits, estimate timescales and equilibrium populations, and willreport on our findings.

X-ray spectroscopy of electronic quasimolecules. I. Isolation and study of particular K molecular-orbital transitions

International Nuclear Information System (INIS)

Liarokapis, E.; Zouros, T.J.M.; Greenberg, J.S.

1987-01-01

Selected K molecular-orbital (MO) transitions in collisions of 100-, 160-, and 200-MeV /sup 93/Nb on /sup 93/Nb and 200-MeV /sup 93/Nb on /sup 120/Sn have been isolated in a MO x-ray--K x-ray coincidence measurement. This experiment exploits the cascade relationship between the MO x rays emitted in transitions from the (2pπ/sub x/, 2pσ) MO's into the 1sσ MO and the characteristic K x ray which follows from the filling of the ensuing vacancy in the projectile or target atoms after their separation. In both symmetric and asymmetric systems, most of the high-energy MO x rays (C2 radiation) were found to be in coincidence with characteristic K x rays while the low-energy MO x rays (C1 radiation) were not correlated to the K x rays. Noncascade processes due to multiple vacancies in the 1sσ and 2pσ MO's were also found to contribute a small amount to the true MO x-ray--K x-ray coincidences. Theoretical estimates of the relative contributions of the isolated transitions as well as contributions from multiple vacancies are discussed

DISCOVERY OF THE PIGTAIL MOLECULAR CLOUD IN THE GALACTIC CENTER

International Nuclear Information System (INIS)

Matsumura, Shinji; Oka, Tomoharu; Tanaka, Kunihiko; Nagai, Makoto; Kamegai, Kazuhisa; Hasegawa, Tetsuo

2012-01-01

This paper reports the discovery of a helical molecular cloud in the central molecular zone (CMZ) of our Galaxy. This 'pigtail' molecular cloud appears at (l, b, V LSR ) ≅ (–0. 0 7, + 0. 0 0, – 70 to –30 km s –1 ), with a spatial size of ∼20 × 20 pc 2 and a mass of (2-6) × 10 5 M ☉ . This is the third helical gaseous nebula found in the Galactic center region to date. Line intensity ratios indicate that the pigtail molecular cloud has slightly higher temperature and/or density than the other normal clouds in the CMZ. We also found a high-velocity wing emission near the footpoint of this cloud. We propose a formation model of the pigtail molecular cloud. It might be associated with a magnetic tube that is twisted and coiled because of the interaction between clouds in the innermost x 1 orbit and ones in the outermost x 2 orbit.

Limiting assumptions in molecular modeling: electrostatics.

Science.gov (United States)

Marshall, Garland R

2013-02-01

Molecular mechanics attempts to represent intermolecular interactions in terms of classical physics. Initial efforts assumed a point charge located at the atom center and coulombic interactions. It is been recognized over multiple decades that simply representing electrostatics with a charge on each atom failed to reproduce the electrostatic potential surrounding a molecule as estimated by quantum mechanics. Molecular orbitals are not spherically symmetrical, an implicit assumption of monopole electrostatics. This perspective reviews recent evidence that requires use of multipole electrostatics and polarizability in molecular modeling.

Orbits

CERN Document Server

Xu, Guochang

2008-01-01

This is the first book of the satellite era which describes orbit theory with analytical solutions of the second order with respect to all possible disturbances. Based on such theory, the algorithms of orbits determination are completely revolutionized.

Orbital Chondroma: A rare mesenchymal tumor of orbit

Directory of Open Access Journals (Sweden)

Ruchi S Kabra

2015-01-01

Full Text Available While relatively common in the skeletal system, cartilaginous tumors are rarely seen originating from the orbit. Here, we report a rare case of an orbital chondroma. A 27-year-old male patient presented with a painless hard mass in the superonasal quadrant (SNQ of left orbit since 3 months. On examination, best-corrected visual acuity of both eyes was 20/20, with normal anterior and posterior segment with full movements of eyeballs and normal intraocular pressure. Computerized tomography scan revealed well defined soft tissue density lesion in SNQ of left orbit. Patient was operated for anteromedial orbitotomy under general anesthesia. Mass was excised intact and sent for histopathological examination (HPE. HPE report showed lobular aggregates of benign cartilaginous cells with mild atypia suggesting of benign cartilaginous tumor - chondroma. Very few cases of orbital chondroma have been reported in literature so far.

Numerical evaluation of two-center integrals over Slater type orbitals

Energy Technology Data Exchange (ETDEWEB)

Kurt, S. A., E-mail: slaykurt@gmail.com [Department of Physics, Natural Sciences Institute, Ondokuz Mayıs University, 55139, Samsun (Turkey); Yükçü, N., E-mail: nyukcu@gmail.com [Department of Energy Systems Engineering, Faculty of Technology, Adıyaman University, 02040, Adıyaman (Turkey)

2016-03-25

Slater Type Orbitals (STOs) which one of the types of exponential type orbitals (ETOs) are used usually as basis functions in the multicenter molecular integrals to better understand physical and chemical properties of matter. In this work, we develop algorithms for two-center overlap and two-center two-electron hybrid and Coulomb integrals which are calculated with help of translation method for STOs and some auxiliary functions by V. Magnasco’s group. We use Mathematica programming language to produce algorithms for these calculations. Numerical results for some quantum numbers are presented in the tables. Consequently, we compare our obtained numerical results with the other known literature results and other details of evaluation method are discussed.

Numerical evaluation of two-center integrals over Slater type orbitals

International Nuclear Information System (INIS)

Kurt, S. A.; Yükçü, N.

2016-01-01

Slater Type Orbitals (STOs) which one of the types of exponential type orbitals (ETOs) are used usually as basis functions in the multicenter molecular integrals to better understand physical and chemical properties of matter. In this work, we develop algorithms for two-center overlap and two-center two-electron hybrid and Coulomb integrals which are calculated with help of translation method for STOs and some auxiliary functions by V. Magnasco’s group. We use Mathematica programming language to produce algorithms for these calculations. Numerical results for some quantum numbers are presented in the tables. Consequently, we compare our obtained numerical results with the other known literature results and other details of evaluation method are discussed.

Studies on EOS of shock-generated argon plasmas

International Nuclear Information System (INIS)

Wang Fanhou; Jing Fuqian

2001-01-01

The equation of state for argon plasma, covering the thermodynamic states of 10000-30000 K in temperature and 0.0133-0.166 GPa in pressure, is computed using the Saha model and Debye-Huckel correction. Comparisons of the measured EOS with the calculated ones demonstrate the Saha model and Debye-Huckel correction can be used to well describe the essential behavior of argon plasma under the thermodynamic condition above-mentioned

Fermi level alignment in molecular nanojunctions and its relation to charge transfer

DEFF Research Database (Denmark)

Stadler, Robert; Jacobsen, Karsten Wedel

2006-01-01

The alignment of the Fermi level of a metal electrode within the gap of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of a molecule is a key quantity in molecular electronics, which can vary the electron transparency of a single-molecule junction...... by orders of magnitude. We present a quantitative analysis of the relation between this level alignment (which can be estimated from charging free molecules) and charge transfer for bipyridine and biphenyl dithiolate (BPDT) molecules attached to gold leads based on density functional theory calculations...... end of the gap in the transmission function for bipyridine and at its lower end for BPDT....

Molecular integrals for exponential-type orbitals using hyperspherical harmonics

DEFF Research Database (Denmark)

Avery, James Emil; Avery, John Scales

2015-01-01

-dimensional hypersphere. Using this projection, Fock was able to show that the Fourier transforms of Coulomb Sturmian basis functions are very simply related to four-dimensional hyperspherical harmonics.With the help of Fock's relationships and the theory of hyperspherical harmonics we are able to evaluate molecular...

Local orbitals by minimizing powers of the orbital variance

DEFF Research Database (Denmark)

Jansik, Branislav; Høst, Stinne; Kristensen, Kasper

2011-01-01

's correlation consistent basis sets, it is seen that for larger penalties, the virtual orbitals become more local than the occupied ones. We also show that the local virtual HF orbitals are significantly more local than the redundant projected atomic orbitals, which often have been used to span the virtual...

Exact and Optimal Quantum Mechanics/Molecular Mechanics Boundaries.

Science.gov (United States)

Sun, Qiming; Chan, Garnet Kin-Lic

2014-09-09

Motivated by recent work in density matrix embedding theory, we define exact link orbitals that capture all quantum mechanical (QM) effects across arbitrary quantum mechanics/molecular mechanics (QM/MM) boundaries. Exact link orbitals are rigorously defined from the full QM solution, and their number is equal to the number of orbitals in the primary QM region. Truncating the exact set yields a smaller set of link orbitals optimal with respect to reproducing the primary region density matrix. We use the optimal link orbitals to obtain insight into the limits of QM/MM boundary treatments. We further analyze the popular general hybrid orbital (GHO) QM/MM boundary across a test suite of molecules. We find that GHOs are often good proxies for the most important optimal link orbital, although there is little detailed correlation between the detailed GHO composition and optimal link orbital valence weights. The optimal theory shows that anions and cations cannot be described by a single link orbital. However, expanding to include the second most important optimal link orbital in the boundary recovers an accurate description. The second optimal link orbital takes the chemically intuitive form of a donor or acceptor orbital for charge redistribution, suggesting that optimal link orbitals can be used as interpretative tools for electron transfer. We further find that two optimal link orbitals are also sufficient for boundaries that cut across double bonds. Finally, we suggest how to construct "approximately" optimal link orbitals for practical QM/MM calculations.

Corrigendum to ;Dipole moment and solvatochromism of benzoic acid liquid crystals: Tuning the dipole moment and molecular orbital energies by substituted Au under external electric field; [J. Mol. Struct. 1137 (2017) 440-452

Science.gov (United States)

Sıdır, Yadigar Gülseven; Sıdır, İsa; Demiray, Ferhat

2017-08-01

The authors regret to inform that three references in the article titled ;Dipole moment and solvatochromism of benzoic acid liquid crystals: Tuning the dipole moment and molecular orbital energies by substituted Au under external electric field; are not given in the manuscript. This is purely an oversight mistake. The references are as shown in this correction. The authors would like to apologize for any inconvenience caused.

Orbital Dynamics of Low-Earth Orbit Laser-Propelled Space Vehicles

International Nuclear Information System (INIS)

Yamakawa, Hiroshi; Funaki, Ikkoh; Komurasaki, Kimiya

2008-01-01

Trajectories applicable to laser-propelled space vehicles with a laser station in low-Earth orbit are investigated. Laser vehicles are initially located in the vicinity of the Earth-orbiting laser station in low-earth orbit at an altitude of several hundreds kilometers, and are accelerated by laser beaming from the laser station. The laser-propelled vehicles start from low-earth orbit and finally escape from the Earth gravity well, enabling interplanetary trajectories and planetary exploration

Momentum distributions and ionization potentials for the valence orbitals of hydrogen fluoride and hydrogen chloride

International Nuclear Information System (INIS)

Brion, C.E.; Hood, S.T.; Suzuki, I.H.; Weigold, E.

1980-02-01

The binding energy spectra and momentum distributions for the valence orbitals of HF and HCl have been obtained using (e,2e) spectroscopy with symmetric kinematics at 1200eV and 400eV. For HCl the strength of the innermost valence orbital (4sigma) is found to be significantly split among several ion states in the range 25eV to 41eV. The corresponding orbital in HF (2sigma) is however not significantly split among ion states. The measured momentum distributions are compared with the results of several calculatons of at least double zeta quality as well as with a one particle Green's function calculation of the generalized overlap amplitude. Agreement in shape is quite good for the innermost orbitals, but for the π and outer sigma orbitals of HF the momentum distributions calculated directly from the molecular orbitals are significantly more extended in momentum space than the measured distributions. The Green's function calculations give momentum distributions in good agreement with the data and pole strengths for transitions in qualitative agreement with the observed cross sections

CONGENITAL ORBITAL TERATOMA

African Journals Online (AJOL)

was done without contrast and 3mm/5mm/10mm slices were obtained to cover the orbit, skull base and brain. The findings included a soft tissue mass arising from the orbit. The left eye ball was extra orbital. There was no defect .... love's Short Practice of Surgery. 7 Edition,. Levis London, 1997; 45-64. 2. Orbital tumor Part 1, ...

16O + 16O molecular structures of superdeformed states in S isotopes

Science.gov (United States)

Taniguchi, Y.

2017-06-01

Structures of excited states in S isotopes are investigated by using the antisymmetrized molecular dynamics and generator coordinate method (GCM). The GCM basis wave functions are calculated via energy variation with a constraint on the quadrupole deformation parameter β. By applying the GCM after parity and angular momentum projections, the coexistence of positive- and negative-parity superdeformed (SD) bands are predicted in 33-36S except for negative-parity states in 36S. The SD bands have structures of 16O + 16O + valence neutron(s) in molecular orbitals around the two 16O cores in a cluster picture. The configurations of the valence neutron(s) in the SD states are δ and/or π molecular orbitals.

APMO: UN PROGRAMA COMPUTACIONAL PARA EL ESTUDIO DE EFECTOS CUÁNTICOS NUCLEARES MEDIANTE LA TEORÍA DEL ORBITAL MOLECULAR ELECTRÓNICO Y NO ELECTRÓNICO.

Directory of Open Access Journals (Sweden)

Sergio González

2009-04-01

Full Text Available Con el fin de estudiar teóricamente fenómenos en donde los núcleos atómicos presentan comportamiento cuántico, hemos desarrollado el paquete computacional APMO (Any-Particle Molecular Orbital. Este implementa el método de orbitales moleculares nucleares y electrónicos (OMNE a un nivel de teoría Hartree-Fock (HF, en el que tanto núcleos como electrones se representan como funciones de onda.Para comprobar la correcta implementación del método, se realizaron  cálculos de estructura electrónica regular y núcleo-electrónica de las moléculas H2 y LiH. Las componentes de energía calculadas siguen las  tendencias y están en el mismo orden de magnitud de cálculos similares reportados en la literatura.A diferencia de otros paquetes que implementan el método OMNE, el nuestro fué diseñado para estudiar sistemas con cualquier número de especies cuánticas. 

Orbital momentum distribution and binding energies for the complete valence shell of molecular bromine

International Nuclear Information System (INIS)

Frost, L.; Grisogono, A.M.; Weigold, E.

1987-08-01

The binding energy spectrum of Br 2 has been recorded in both the outer and inner valence regions using electron momentum spectroscopy. The measurements are compared with the results of several Green's function calculations using different approximations and based on both polarized and unpolarized wave functions. The inner valence region, observed for the first time, is found to exhibit complex structure that is shown to be due to many-body effects, thus indicating a breakdown of the simple MO picture for ionization in this region. Momentum distributions for the three outer valence orbitals are also measured and compared with spherically averaged calculations using the target Hartree-Fock and plane wave impulse approximations. The effect of polarization functions in the basis set is investigated. Orbital density maps in both momentum and position space have been calculated and compared with the experimental measurements

Structural characterization of MAO and related aluminum complexes. 1. Solid-state (27)Al NMR with comparison to EFG tensors from ab initio molecular orbital calculations.

Science.gov (United States)

Bryant, P L; Harwell, C R; Mrse, A A; Emery, E F; Gan, Z; Caldwell, T; Reyes, A P; Kuhns, P; Hoyt, D W; Simeral, L S; Hall, R W; Butler, L G

2001-12-05

Experimental and ab initio molecular orbital techniques are developed for study of aluminum species with large quadrupole coupling constants to test structural models for methylaluminoxanes (MAO). The techniques are applied to nitrogen- and oxygen-containing complexes of aluminum and to solid MAO isolated from active commercial MAO preparations. (Aminato)- and (propanolato)aluminum clusters with 3-, 4-, and 6-coordinate aluminum sites are studied with three (27)Al NMR techniques optimized for large (27)Al quadrupole coupling constants: field-swept, frequency-stepped, and high-field MAS NMR. Four-membered (aminato)aluminum complexes with AlN(4) coordination yield slightly smaller C(q) values than similar AlN(2)C(2) sites: 12.2 vs 15.8 MHz. Planar 3-coordinate AlN(2)C sites have the largest C(q) values, 37 MHz. In all cases, molecular orbital calculations of the electric field gradient tensors yields C(q) and eta values that match with experiment, even for a large hexameric (aminato)aluminum cage. A D(3d) symmetry hexaaluminum oxane cluster, postulated as a model for MAO, yields a calculated C(q) of -23.7 MHz, eta = 0.7474, and predicts a spectrum that is too broad to match the field-swept NMR of methylaluminoxane, which shows at least three sites, all with C(q) values greater than 15 MHz but less than 21 MHz. Thus, the proposed hexaaluminum cluster, with its strained four-membered rings, is not a major component of MAO. However, calculations for dimers of the cage complex, either edge-bridged or face-bridged, show a much closer match to experiment. Also, MAO preparations differ, with a gel form of MAO having significantly larger (27)Al C(q) values than a nongel form, a conclusion reached on the basis of (27)Al NMR line widths in field-swept NMR spectra acquired from 13 to 24 T.

Radiovolumetry of the orbit

International Nuclear Information System (INIS)

Abujamra, S.

1983-01-01

The authors present a method called ''Radiovolumetry of the orbit'' that permits the evaluation of the orbital volume from anteroposterior skull X-Rays (CALDWELL 30 0 position). The research was based in the determination of the orbital volume with lead spheres, in 1010 orbits of 505 dry skulls of Anatomy Museums. After the dry skulls was X-rayed six frontal orbital diameters were made, with care to correct the radiographic amplification. PEARSON correlation coeficient test was applied between the mean orbital diameter and the orbital volume. The result was r = 0,8 with P [pt

DFT Study of the Structure, Reactivity, Natural Bond Orbital and Hyperpolarizability of Thiazole Azo Dyes

Directory of Open Access Journals (Sweden)

Osman I. Osman

2017-02-01

Full Text Available The structure, reactivity, natural bond orbital (NBO, linear and nonlinear optical (NLO properties of three thiazole azo dyes (A, B and C were monitored by applying B3LYP, CAM-B3LYP and ωB97XD functionals with 6-311++G** and aug-cc-pvdz basis sets. The geometrical parameters,dipolemoments,HOMO-LUMO(highest occupied molecular orbital,lowest unoccupied molecular orbital energy gaps, absorption wavelengths and total hyperpolarizabilities were investigated in carbon tetrachloride (CCl4 chloroform (CHCl3, dichloromethane (CH2Cl2 and dimethlysulphoxide (DMSO. The donor methoxyphenyl group deviates from planarity with the thiazole azo moiety by ca. 38◦; while the acceptor dicyanovinyl, indandione and dicyanovinylindanone groups diverge by ca. 6◦. The HOMOs for the three dyes are identical. They spread over the methoxyphenyl donor moiety, the thiazole and benzene rings as π-bonding orbitals. The LUMOs are shaped up by the nature of the acceptor moieties. The LUMOs of the A, B and C dyes extend over the indandione, malononitrile and dicyanovinylindanone acceptor moieties, respectively, as π-antibonding orbitals. The HOMO-LUMO splittings showed that Dye C is much more reactive than dyes A and B. Compared to dyes A and B, Dye C yielded a longer maximum absorption wavelength because of the stabilization of its LUMOs relative to those of the other two. The three dyes show solvatochromism accompanied by significant increases in hyperpolarizability. The enhancement of the total hyperpolarizability of C compared to those of A and B is due to the cumulative action of the long π-conjugation of the indanone ring and the stronger electron-withdrawing ability of the dicyanovinyl moiety that form the dicyanovinylindanone acceptor group. These findings are facilitated by a natural bond orbital (NBO technique. The very high total hyperpolarizabilities of the three dyes define their potent nonlinear optical (NLO behaviour.

Basis set construction for molecular electronic structure theory: natural orbital and Gauss-Slater basis for smooth pseudopotentials.

Science.gov (United States)

Petruzielo, F R; Toulouse, Julien; Umrigar, C J

2011-02-14

A simple yet general method for constructing basis sets for molecular electronic structure calculations is presented. These basis sets consist of atomic natural orbitals from a multiconfigurational self-consistent field calculation supplemented with primitive functions, chosen such that the asymptotics are appropriate for the potential of the system. Primitives are optimized for the homonuclear diatomic molecule to produce a balanced basis set. Two general features that facilitate this basis construction are demonstrated. First, weak coupling exists between the optimal exponents of primitives with different angular momenta. Second, the optimal primitive exponents for a chosen system depend weakly on the particular level of theory employed for optimization. The explicit case considered here is a basis set appropriate for the Burkatzki-Filippi-Dolg pseudopotentials. Since these pseudopotentials are finite at nuclei and have a Coulomb tail, the recently proposed Gauss-Slater functions are the appropriate primitives. Double- and triple-zeta bases are developed for elements hydrogen through argon. These new bases offer significant gains over the corresponding Burkatzki-Filippi-Dolg bases at various levels of theory. Using a Gaussian expansion of the basis functions, these bases can be employed in any electronic structure method. Quantum Monte Carlo provides an added benefit: expansions are unnecessary since the integrals are evaluated numerically.

Spin and charge controlled by antisymmetric spin-orbit coupling in a triangular-triple-quantum-dot Kondo system

Science.gov (United States)

Koga, M.; Matsumoto, M.; Kusunose, H.

2018-05-01

We study a local antisymmetric spin-orbit (ASO) coupling effect on a triangular-triple-quantum-dot (TTQD) system as a theoretical proposal for a new application of the Kondo physics to nanoscale devices. The electric polarization induced by the Kondo effect is strongly correlated with the spin configurations and molecular orbital degrees of freedom in the TTQD. In particular, an abrupt sign reversal of the emergent electric polarization is associated with a quantum critical point in a magnetic field, which can also be controlled by the ASO coupling that changes the mixing weight of different orbital components in the TTQD ground state.

MCSCF optimization through combined use of natural orbitals and the Brillouin-Levy-Berthier theorem

International Nuclear Information System (INIS)

Ruedenberg, K.; Cheung, L.M.; Elbert, S.T.

1979-01-01

A novel approach is developed for optimizing molecular orbitals within the context of a multiconfiguration self-consistent-field problem. The MCSCF wave function is determined through a sequence of eigenvalue problems in the multiconfiguration space and the single-excitation space. They are used iteratively to improve the natural orbitals, which in turn are related, by successively improved transformations, to the MCSCF orbitals. The mathematical problems arising out of this general concept are solved and the computational implementation is discussed. In many applications the method has proven itself as a powerful approach in forcing rapid convergence. Adaptation to spin and spatial symmetry is maintained throughout, and the procedure is applicable to excited states as well as to ground states. 3 figures, 2 tables

A method of orbital analysis for large-scale first-principles simulations

Energy Technology Data Exchange (ETDEWEB)

Ohwaki, Tsukuru [Advanced Materials Laboratory, Nissan Research Center, Nissan Motor Co., Ltd., 1 Natsushima-cho, Yokosuka, Kanagawa 237-8523 (Japan); Otani, Minoru [Nanosystem Research Institute, National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Ibaraki 305-8568 (Japan); Ozaki, Taisuke [Research Center for Simulation Science (RCSS), Japan Advanced Institute of Science and Technology (JAIST), 1-1 Asahidai, Nomi, Ishikawa 923-1292 (Japan)

2014-06-28

An efficient method of calculating the natural bond orbitals (NBOs) based on a truncation of the entire density matrix of a whole system is presented for large-scale density functional theory calculations. The method recovers an orbital picture for O(N) electronic structure methods which directly evaluate the density matrix without using Kohn-Sham orbitals, thus enabling quantitative analysis of chemical reactions in large-scale systems in the language of localized Lewis-type chemical bonds. With the density matrix calculated by either an exact diagonalization or O(N) method, the computational cost is O(1) for the calculation of NBOs associated with a local region where a chemical reaction takes place. As an illustration of the method, we demonstrate how an electronic structure in a local region of interest can be analyzed by NBOs in a large-scale first-principles molecular dynamics simulation for a liquid electrolyte bulk model (propylene carbonate + LiBF{sub 4})

A method of orbital analysis for large-scale first-principles simulations

International Nuclear Information System (INIS)

Ohwaki, Tsukuru; Otani, Minoru; Ozaki, Taisuke

2014-01-01

An efficient method of calculating the natural bond orbitals (NBOs) based on a truncation of the entire density matrix of a whole system is presented for large-scale density functional theory calculations. The method recovers an orbital picture for O(N) electronic structure methods which directly evaluate the density matrix without using Kohn-Sham orbitals, thus enabling quantitative analysis of chemical reactions in large-scale systems in the language of localized Lewis-type chemical bonds. With the density matrix calculated by either an exact diagonalization or O(N) method, the computational cost is O(1) for the calculation of NBOs associated with a local region where a chemical reaction takes place. As an illustration of the method, we demonstrate how an electronic structure in a local region of interest can be analyzed by NBOs in a large-scale first-principles molecular dynamics simulation for a liquid electrolyte bulk model (propylene carbonate + LiBF 4 )

Orbital wall fractures

International Nuclear Information System (INIS)

Iinuma, Toshitaka; Ishio, Ken-ichirou; Yoshinami, Hiroyoshi; Kuriyama, Jun-ichi; Hirota, Yoshiharu.

1993-01-01

A total of 59 cases of mild facial fractures (simple orbital wall fractures, 34 cases, other facial fractures, 25 cases) with the clinical suspects of orbital wall fractures were evaluated both by conventional views (Waters' and Caldwell views) and coronal CT scans. Conventional views were obtained, as an average, after 4 days and CT after 7 days of injuries. Both the medial wall and the floor were evaluated at two sites, i.e., anterior and posterior. The ethmoid-maxillary plate was also included in the study. The degree of fractures was classified as, no fractures, fractures of discontinuity, dislocation and fragmentation. The coronal CT images in bone window condition was used as reference and the findings were compared between conventional views and CT. The correct diagnosis was obtained as follows: orbital floor (anterior, 78%, posterior, 73%), medial orbital wall (anterior, 72%, posterior, 72%) and ethmoid-maxillary plate (64%). The false positive diagnosis was as follows: orbital floor (anterior only, 13%), medial orbital wall (anterior only, 7%) and ethmoid-maxillary plate (11%). The false negative diagnosis was as follows: orbital floor (anterior, 9%, posterior, 10%), medial orbital wall (anterior, 21%, posterior, 28%) and ethmoid-maxillary plate (21%). The results were compared with those of others in the past. (author)

Analytical and molecular dynamical investigations of the influence of molecular vibrations upon the (e,2e) electron momentum distributions of furan

International Nuclear Information System (INIS)

Morini, F; Deleuze, M S; Watanabe, N; Takahashi, M

2015-01-01

The role of molecular vibrations has been theoretically investigated in the electronic ground state on the (e, 2e) valence orbital momentum profiles of furan by means of two complementary approaches. The first one relies upon the principles of Born-Oppenheimer Molecular Dynamics (BOMD), whereas the second one, referred as Harmonic Analytical Quantum Mechanical (HAQM) approach, includes on quantum-mechanical (paper)

The EDGE-CALIFA survey: the influence of galactic rotation on the molecular depletion time across the Hubble sequence

Science.gov (United States)

Colombo, D.; Kalinova, V.; Utomo, D.; Rosolowsky, E.; Bolatto, A. D.; Levy, R. C.; Wong, T.; Sanchez, S. F.; Leroy, A. K.; Ostriker, E.; Blitz, L.; Vogel, S.; Mast, D.; García-Benito, R.; Husemann, B.; Dannerbauer, H.; Ellmeier, L.; Cao, Y.

2018-04-01

We present a kpc-scale analysis of the relationship between the molecular depletion time (τ^mol_dep) and the orbital time (τorb) across the field of 39 face-on local galaxies, selected from the EDGE-CALIFA sample. We find that, on average, 5 per cent of the available molecular gas is converted into stars per orbital time, or τ^mol_dep˜ 20 τ_orb. The resolved relation shows a scatter of ˜0.5 dex. The scatter is ascribable to galaxies of different morphologies that follow different τ^mol_dep-τorb relations which decrease in steepness from early- to late types. The morphologies appear to be linked with the star formation rate surface density, the molecular depletion time, and the orbital time, but they do not correlate with the molecular gas content of the galaxies in our sample. We speculate that in our molecular gas rich, early-type galaxies, the morphological quenching (in particular the disc stabilization via shear), rather than the absence of molecular gas, is the main factor responsible for their current inefficient star formation.

Determination of Structures and Energetics of Small- and Medium-Sized One-Carbon-Bridged Twisted Amides using ab Initio Molecular Orbital Methods: Implications for Amidic Resonance along the C-N Rotational Pathway.

Science.gov (United States)

Szostak, Roman; Aubé, Jeffrey; Szostak, Michal

2015-08-21

Twisted amides containing nitrogen at the bridgehead position are attractive practical prototypes for the investigation of the electronic and structural properties of nonplanar amide linkages. Changes that occur during rotation around the N-C(O) axis in one-carbon-bridged twisted amides have been studied using ab initio molecular orbital methods. Calculations at the MP2/6-311++G(d,p) level performed on a set of one-carbon-bridged lactams, including 20 distinct scaffolds ranging from [2.2.1] to [6.3.1] ring systems, with the C═O bond on the shortest bridge indicate significant variations in structures, resonance energies, proton affinities, core ionization energies, frontier molecular orbitals, atomic charges, and infrared frequencies that reflect structural changes corresponding to the extent of resonance stabilization during rotation along the N-C(O) axis. The results are discussed in the context of resonance theory and activation of amides toward N-protonation (N-activation) by distortion. This study demonstrates that one-carbon-bridged lactams-a class of readily available, hydrolytically robust twisted amides-are ideally suited to span the whole spectrum of the amide bond distortion energy surface. Notably, this study provides a blueprint for the rational design and application of nonplanar amides in organic synthesis. The presented findings strongly support the classical amide bond resonance model in predicting the properties of nonplanar amides.

Charge-spin-orbital dynamics of one-dimensional two-orbital Hubbard model

Energy Technology Data Exchange (ETDEWEB)

Onishi, Hiroaki [Advanced Science Research Center, Japan Atomic Energy Agency, Tokai, Ibaraki 319-1195 (Japan)

2010-01-15

We study the real-time evolution of a charge-excited state in a one-dimensional e{sub g}-orbital degenerate Hubbard model, by a time-dependent density-matrix renormalization group method. Considering a chain along the z direction, electrons hop between adjacent 3z{sup 2}-r{sup 2} orbitals, while x{sup 2}-y{sup 2} orbitals are localized. For the charge-excited state, a holon-doublon pair is introduced into the ground state at quarter filling. At initial time, there is no electron in a holon site, while a pair of electrons occupies 3z{sup 2}-r{sup 2} orbital in a doublon site. As the time evolves, the holon motion is governed by the nearest-neighbor hopping, but the electron pair can transfer between 3z{sup 2}-r{sup 2} orbital and x{sup 2}-y{sup 2} orbital through the pair hopping in addition to the nearest-neighbor hopping. Thus holon and doublon propagate at different speed due to the pair hopping that is characteristic of multi-orbital systems.

Modeling the Exo-Brake and the Development of Strategies for De-Orbit Drag Modulation

Science.gov (United States)

Murbach, M. S.; Papadopoulos, P.; Glass, C.; Dwyer-Cianciolo, A.; Powell, R. W.; Dutta, S.; Guarneros-Luna, A.; Tanner, F. A.; Dono, A.

2016-01-01

The Exo-Brake is a simple, non-propulsive means of de-orbiting small payloads from orbital platforms such as the International Space Station (ISS). Two de-orbiting experiments with fixed surface area Exo-Brakes have been successfully conducted in the last two years on the TechEdSat-3 and -4 nano-satellite missions. The development of the free molecular flow aerodynamic data-base is presented in terms of angle of attack, projected front surface area variation, and altitude. Altitudes are considered ranging from the 400km ISS jettison altitude to 90km. Trajectory tools are then used to predict de-orbit/entry corridors with the inclusion of the key atmospheric and geomagnetic uncertainties. Control system strategies are discussed which will be applied to the next two planned TechEdSat-5 and -6 nano-satellite missions - thus increasing the targeting accuracy at the Von Karman altitude through the proposed drag modulation technique.

Traumatic orbital CSF leak

Science.gov (United States)

Borumandi, Farzad

2013-01-01

Compared to the cerebrospinalfluid (CSF) leak through the nose and ear, the orbital CSF leak is a rare and underreported condition following head trauma. We present the case of a 49-year-old woman with oedematous eyelid swelling and ecchymosis after a seemingly trivial fall onto the right orbit. Apart from the above, she was clinically unremarkable. The CT scan revealed a minimally displaced fracture of the orbital roof with no emphysema or intracranial bleeding. The fractured orbital roof in combination with the oedematous eyelid swelling raised the suspicion for orbital CSF leak. The MRI of the neurocranium demonstrated a small-sized CSF fistula extending from the anterior cranial fossa to the right orbit. The patient was treated conservatively and the lid swelling resolved completely after 5 days. Although rare, orbital CSF leak needs to be included in the differential diagnosis of periorbital swelling following orbital trauma. PMID:24323381

Antisymmetrized molecular dynamics studies for exotic clustering phenomena in neutron-rich nuclei

Energy Technology Data Exchange (ETDEWEB)

Kimura, M. [Hokkaido University, Department of Physics, Sapporo (Japan); Hokkaido University, Nuclear Reaction Data Centre, Faculty of Science, Sapporo (Japan); Suhara, T. [Matsue College of Technology, Matsue (Japan); Kanada-En' yo, Y. [Kyoto University, Department of Physics, Kyoto (Japan)

2016-12-15

We present a review of recent works on clustering phenomena in unstable nuclei studied by antisymmetrized molecular dynamics (AMD). The AMD studies in these decades have uncovered novel types of clustering phenomena brought about by the excess neutrons. Among them, this review focuses on the molecule-like structure of unstable nuclei. One of the earliest discussions on the clustering in unstable nuclei was made for neutron-rich Be and B isotopes. AMD calculations predicted that the ground state clustering is enhanced or reduced depending on the number of excess neutrons. Today, the experiments are confirming this prediction as the change of the proton radii. Behind this enhancement and reduction of the clustering, there are underlying shell effects called molecular and atomic orbits. These orbits form covalent and ionic bonding of the clusters analogous to the atomic molecules. It was found that this ''molecular-orbit picture'' reasonably explains the low-lying spectra of Be isotopes. The molecular-orbit picture is extended to other systems having parity asymmetric cluster cores and to the three cluster systems. O and Ne isotopes are the candidates of the former, while the 3α linear chains in C isotopes are the latter. For both subjects, many intensive studies are now in progress. We also pay a special attention to the observables which are the fingerprint of the clustering. In particular, we focus on the monopole and dipole transitions which are recently regarded as good probe for the clustering. We discuss how they have and will reveal the exotic clustering. (orig.)

Dynamic analysis of electron density in the course of the internal motion of molecular system

International Nuclear Information System (INIS)

Tachibana, A.; Hori, K.; Asai, Y.; Yamabe, T.

1984-01-01

The general dynamic aspect of electron density of a molecular system is studied on the basis of the general equation of the electron orbital which is formulated for the dynamic study of electronic motion. The newly defined electron orbital incorporates the dynamics of molecular vibration into the electronic structures. In this scheme, the change of electron distribution caused by excitation of vibrational state is defined as the ''dynamic electron transfer.'' The dynamic electron density is found to have the remarkable ''additive'' property. The time-dependent aspect of the dynamic electron redistribution is also analyzed on the basis of the ''coherent state.'' The new method relates the classical vibrational amplitude to the quantum number of the vibrational state. As a preliminary application of the present treatment, the dynamic electron densities of H 2 , HD, HT, HF, and HCl molecules are calculated by use of ab initio molecular orbital method

Orbitals from local RDMFT: Are they Kohn-Sham or natural orbitals?

International Nuclear Information System (INIS)

Theophilou, Iris; Helbig, Nicole; Lathiotakis, Nektarios N.; Gidopoulos, Nikitas I.; Rubio, Angel

2015-01-01

Recently, an approximate theoretical framework was introduced, called local reduced density matrix functional theory (local-RDMFT), where functionals of the one-body reduced density matrix (1-RDM) are minimized under the additional condition that the optimal orbitals satisfy a single electron Schrödinger equation with a local potential. In the present work, we focus on the character of these optimal orbitals. In particular, we compare orbitals obtained by local-RDMFT with those obtained with the full minimization (without the extra condition) by contrasting them against the exact NOs and orbitals from a density functional calculation using the local density approximation (LDA). We find that the orbitals from local-RMDFT are very close to LDA orbitals, contrary to those of the full minimization that resemble the exact NOs. Since local RDMFT preserves the good quality of the description of strong static correlation, this finding opens the way to a mixed density/density matrix scheme, where Kohn-Sham orbitals obtain fractional occupations from a minimization of the occupation numbers using 1-RDM functionals. This will allow for a description of strong correlation at a cost only minimally higher than a density functional calculation

Role of orbital dynamics and cloud-cloud collisions in the formation of giant molecular clouds in global spiral structures

International Nuclear Information System (INIS)

Roberts, W.W. Jr.; Stewart, G.R.

1987-01-01

The role of orbit crowding and cloud-cloud collisions in the formation of GMCs and their organization in global spiral structure is investigated. Both N-body simulations of the cloud system and a detailed analysis of individual particle orbits are used to develop a conceptual understanding of how individual clouds participate in the collective density response. Detailed comparisons are made between a representative cloud-particle simulation in which the cloud particles collide inelastically with one another and give birth to and subsequently interact with young star associations and stripped down simulations in which the cloud particles are allowed to follow ballistic orbits in the absence of cloud-cloud collisions or any star formation processes. Orbit crowding is then related to the behavior of individual particle trajectories in the galactic potential field. The conceptual picture of how GMCs are formed in the clumpy ISMs of spiral galaxies is formulated, and the results are compared in detail with those published by other authors. 68 references

Antisymmetric Orbit Functions

Directory of Open Access Journals (Sweden)

Anatoliy Klimyk

2007-02-01

Full Text Available In the paper, properties of antisymmetric orbit functions are reviewed and further developed. Antisymmetric orbit functions on the Euclidean space $E_n$ are antisymmetrized exponential functions. Antisymmetrization is fulfilled by a Weyl group, corresponding to a Coxeter-Dynkin diagram. Properties of such functions are described. These functions are closely related to irreducible characters of a compact semisimple Lie group $G$ of rank $n$. Up to a sign, values of antisymmetric orbit functions are repeated on copies of the fundamental domain $F$ of the affine Weyl group (determined by the initial Weyl group in the entire Euclidean space $E_n$. Antisymmetric orbit functions are solutions of the corresponding Laplace equation in $E_n$, vanishing on the boundary of the fundamental domain $F$. Antisymmetric orbit functions determine a so-called antisymmetrized Fourier transform which is closely related to expansions of central functions in characters of irreducible representations of the group $G$. They also determine a transform on a finite set of points of $F$ (the discrete antisymmetric orbit function transform. Symmetric and antisymmetric multivariate exponential, sine and cosine discrete transforms are given.

Fullerene/layered antiferromagnetic reconstructed spinterface: Subsurface layer dominates molecular orbitals' spin-split and large induced magnetic moment

Science.gov (United States)

Shao, Yangfan; Pang, Rui; Pan, Hui; Shi, Xingqiang

2018-03-01

The interfaces between organic molecules and magnetic metals have gained increasing interest for both fundamental reasons and applications. Among them, the C60/layered antiferromagnetic (AFM) interfaces have been studied only for C60 bonded to the outermost ferromagnetic layer [S. L. Kawahara et al., Nano Lett. 12, 4558 (2012) and D. Li et al., Phys. Rev. B 93, 085425 (2016)]. Here, via density functional theory calculations combined with evidence from the literature, we demonstrate that C60 adsorption can reconstruct the layered-AFM Cr(001) surface at elevated annealing temperatures so that C60 bonds to both the outermost and the subsurface Cr layers in opposite spin directions. Surface reconstruction drastically changes the adsorbed molecule spintronic properties: (1) the spin-split p-d hybridization involves multi-orbitals of C60 and top two layers of Cr with opposite spin-polarization, (2) the subsurface Cr atom dominates the C60 electronic properties, and (3) the reconstruction induces a large magnetic moment of 0.58 μB in C60 as a synergistic effect of the top two Cr layers. The induced magnetic moment in C60 can be explained by the magnetic direct-exchange mechanism, which can be generalized to other C60/magnetic metal systems. Understanding these complex hybridization behaviors is a crucial step for molecular spintronic applications.

Angles-only relative orbit determination in low earth orbit

Science.gov (United States)

Ardaens, Jean-Sébastien; Gaias, Gabriella

2018-06-01

The paper provides an overview of the angles-only relative orbit determination activities conducted to support the Autonomous Vision Approach Navigation and Target Identification (AVANTI) experiment. This in-orbit endeavor was carried out by the German Space Operations Center (DLR/GSOC) in autumn 2016 to demonstrate the capability to perform spaceborne autonomous close-proximity operations using solely line-of-sight measurements. The images collected onboard have been reprocessed by an independent on-ground facility for precise relative orbit determination, which served as ultimate instance to monitor the formation safety and to characterize the onboard navigation and control performances. During two months, several rendezvous have been executed, generating a valuable collection of images taken at distances ranging from 50 km to only 50 m. Despite challenging experimental conditions characterized by a poor visibility and strong orbit perturbations, angles-only relative positioning products could be continuously derived throughout the whole experiment timeline, promising accuracy at the meter level during the close approaches. The results presented in the paper are complemented with former angles-only experience gained with the PRISMA satellites to better highlight the specificities induced by different orbits and satellite designs.

On a mass independent approach leading to planetary orbit discretization

International Nuclear Information System (INIS)

Oliveira Neto, Marcal de

2007-01-01

The present article discusses a possible fractal approach for understanding orbit configurations around a central force field in well known systems of our infinitely small and infinitely large universes, based on quantum atomic models. This approach is supported by recent important theoretical investigations reported in the literature. An application presents a study involving the three star system HD 188753 Cygni in an approach similar to that employed in molecular quantum mechanics investigations

Edge-on gating effect in molecular wires.

Science.gov (United States)

Lo, Wai-Yip; Bi, Wuguo; Li, Lianwei; Jung, In Hwan; Yu, Luping

2015-02-11

This work demonstrates edge-on chemical gating effect in molecular wires utilizing the pyridinoparacyclophane (PC) moiety as the gate. Different substituents with varied electronic demands are attached to the gate to simulate the effect of varying gating voltages similar to that in field-effect transistor (FET). It was observed that the orbital energy level and charge carrier's tunneling barriers can be tuned by changing the gating group from strong electron acceptors to strong electron donors. The single molecule conductance and current-voltage characteristics of this molecular system are truly similar to those expected for an actual single molecular transistor.

Orbital fractures: a review

Directory of Open Access Journals (Sweden)

Jeffrey M Joseph

2011-01-01

Full Text Available Jeffrey M Joseph, Ioannis P GlavasDivision of Ophthalmic Plastic and Reconstructive Surgery, Department of Ophthalmology, School of Medicine, New York University, New York, NY, USA; Manhattan Eye, Ear, and Throat Hospital, New York, NY, USAAbstract: This review of orbital fractures has three goals: 1 to understand the clinically relevant orbital anatomy with regard to periorbital trauma and orbital fractures, 2 to explain how to assess and examine a patient after periorbital trauma, and 3 to understand the medical and surgical management of orbital fractures. The article aims to summarize the evaluation and management of commonly encountered orbital fractures from the ophthalmologic perspective and to provide an overview for all practicing ophthalmologists and ophthalmologists in training.Keywords: orbit, trauma, fracture, orbital floor, medial wall, zygomatic, zygomatic complex, zmc fracture, zygomaticomaxillary complex fractures 

Molecular cluster theory of chemical bonding in actinide oxide

International Nuclear Information System (INIS)

Ellis, D.E.; Gubanov, V.A.; Rosen, A.

1978-01-01

The electronic structure of actinide monoxides AcO and dioxides AcO 2 , where Ac = Th, U, Np, Pu, Am, Cm and Bk has been studied by molecular cluster methods based on the first-principles one-electron local density theory. Molecular orbitals for nearest neighbor clusters AcO 10- 6 and AcO 12- 8 representative of monoxide and dioxide lattices were obtained using non-relativistic spin-restricted and spin-polarized Hartree-Fock-Slater models for the entire series. Fully relativistic Dirac-Slater calculations were performed for ThO, UO and NpO in order to explore magnitude of spin-orbit splittings and level shifts in valence structure. Self-consistent iterations were carried out for NpO, in which the NpO 6 cluster was embedded in the molecular field of the solid. Finally, a ''moment polarized'' model which combines both spin-polarization and relativistic effects in a consistent fashion was applied to the NpO system. Covalent mixing of oxygen 2p and Ac 5f orbitals was found to increase rapidly across the actinide series; metal s,p,d covalency was found to be nearly constant. Mulliken atomic population analysis of cluster eigenvectors shows that free-ion crystal field models are unreliable, except for the light actinides. X-ray photoelectron line shapes have been calculated and are found to compare rather well with experimental data on the dioxides

Peripheral orbit model

CERN Document Server

Hara, Yasuo

1975-01-01

Peripheral orbit model, in which an incoming hadron is assumed to revolve in a peripheral orbit around a target hadron, is discussed. The non-diffractive parts of two-body reaction amplitudes of hadrons are expressed in terms of the radius, width an absorptivity of the orbit. The radius of the orbit is about 1 fm and the width of the orbit is determined by the range of the interaction between the hadrons. The model reproduces all available experimental data on differential cross-sections and polarizations of $K^{-}p\\to K^{-}p$ and $\\bar K^{\\circ}n$ reactions for all angles successfully. This contribution is not included in the proceedings since it will appear in Progress of Theoretical Physics Vol. 51 (1974) No 2. Any person interested in the subject may apply for reprints to the author.

Orbital transport

International Nuclear Information System (INIS)

Oertel, H. Jr.; Koerner, H.

1993-01-01

The Third Aerospace Symposium in Braunschweig presented, for the first time, the possibility of bringing together the classical disciplines of aerospace engineering and the natural science disciplines of meteorology and air chemistry in a european setting. In this way, aspects of environmental impact on the atmosphere could be examined quantitatively. An essential finding of the european conference, is the unrestricted agreement of the experts that the given launch frequencies of the present orbital transport result in a negligible amount of pollutants being released in the atmosphere. The symposium does, however, call attention to the increasing need to consider the effect of orbital and atmospheric environmental impact of a future increase in launch frequencies of orbital transport in connection with future space stations. The Third Aerospace Symposium, 'Orbital Transport, Technical, Meteorological and Chemical Aspects', constituted a first forum of discussion for engineers and scientists. Questions of new orbital transport technologies and their environmental impact were to be discussed towards a first consensus. Through the 34 reports and articles, the general problems of space transportation and environmental protection were addressed, as well as particular aspects of high temperatures during reentry in the atmosphere of the earth, precision navigation of flight vehicles or flow behavior and air chemistry in the stratosphere. (orig./CT). 342 figs

Orbital apex syndrome associated with fractures of the inferomedial orbital wall

Directory of Open Access Journals (Sweden)

Sugamata A

2013-03-01

Full Text Available Akira SugamataDepartment of Plastic and Reconstructive Surgery, Tokyo Medical University Hachioji Medical Center, Tokyo, JapanAbstract: Although trauma is one of the main causes of orbital apex syndrome (OAS, reports of OAS associated with orbital fractures are relatively rare. We recently treated two patients who sustained severe visual impairment with damage to multiple cranial nerves (third to sixth associated with inferomedial orbital wall fractures. In these patients, posterior movement of the globe caused neuropathy of the cranial and optic nerves by posterior globe edema and hemorrhage, or direct impact between the globe and wall, which might then have induced OAS in the cases described in this report. Steroid therapy was unsuccessful for optic neuropathy due to the delay between injury and administration. When treating patients with inferomedial orbital blowout fractures due to globe-to-wall contact, it is necessary to routinely assess and monitor visual acuity since there may be a delay between the injury and OAS onset.Keywords: orbital apex syndrome, orbital fracture, blowout fracture, optic nerve, globe-to-wall contact mechanism

Electrochemical control of quantum interference in anthraquinone-based molecular switches

DEFF Research Database (Denmark)

Markussen, Troels; Schiøtz, Jakob; Thygesen, Kristian Sommer

2010-01-01

Using first-principles calculations we analyze the electronic transport properties of a recently proposed anthraquinone-based electrochemical switch. Robust conductance on/off ratios of several orders of magnitude are observed due to destructive quantum interference present in the anthraquinone...... of hopping via the localized orbitals. The topology of the tight-binding model, which is dictated by the symmetries of the molecular orbitals, determines the amount of quantum interference....

On the atmospheric drag in orbit determination for low Earth orbit

Science.gov (United States)

Tang, Jingshi; Liu, Lin; Miao, Manqian

2012-07-01

The atmosphere model is always a major limitation for low Earth orbit (LEO) in orbit prediction and determination. The accelerometer can work around the non-gravitational perturbations in orbit determination, but it helps little to improve the atmosphere model or to predict the orbit. For certain satellites, there may be some specific software to handle the orbit problem. This solution can improve the orbit accuracy for both prediction and determination, yet it always contains empirical terms and is exclusive for certain satellites. This report introduces a simple way to handle the atmosphere drag for LEO, which does not depend on instantaneous atmosphere conditions and improves accuracy of predicted orbit. This approach, which is based on mean atmospheric density, is supported by two reasons. One is that although instantaneous atmospheric density is very complicated with time and height, the major pattern is determined by the exponential variation caused by hydrostatic equilibrium and periodic variation caused by solar radiation. The mean density can include the major variations while neglect other minor details. The other reason is that the predicted orbit is mathematically the result from integral and the really determinant factor is the mean density instead of instantaneous density for every time and spot. Using the mean atmospheric density, which is mainly determined by F10.7 solar flux and geomagnetic index, can be combined into an overall parameter B^{*} = C_{D}(S/m)ρ_{p_{0}}. The combined parameter contains several less accurate parameters and can be corrected during orbit determination. This approach has been confirmed in various LEO computations and an example is given below using Tiangong-1 spacecraft. Precise orbit determination (POD) is done using one-day GPS positioning data without any accurate a-priori knowledge on spacecraft or atmosphere conditions. Using the corrected initial state vector of the spacecraft and the parameter B^* from POD, the

Space station orbit maintenance

Science.gov (United States)

Kaplan, D. I.; Jones, R. M.

1983-01-01

The orbit maintenance problem is examined for two low-earth-orbiting space station concepts - the large, manned Space Operations Center (SOC) and the smaller, unmanned Science and Applications Space Platform (SASP). Atmospheric drag forces are calculated, and circular orbit altitudes are selected to assure a 90 day decay period in the event of catastrophic propulsion system failure. Several thrusting strategies for orbit maintenance are discussed. Various chemical and electric propulsion systems for orbit maintenance are compared on the basis of propellant resupply requirements, power requirements, Shuttle launch costs, and technology readiness.

Orbit error characteristic and distribution of TLE using CHAMP orbit data

Science.gov (United States)

Xu, Xiao-li; Xiong, Yong-qing

2018-02-01

Space object orbital covariance data is required for collision risk assessments, but publicly accessible two line element (TLE) data does not provide orbital error information. This paper compared historical TLE data and GPS precision ephemerides of CHAMP to assess TLE orbit accuracy from 2002 to 2008, inclusive. TLE error spatial variations with longitude and latitude were calculated to analyze error characteristics and distribution. The results indicate that TLE orbit data are systematically biased from the limited SGP4 model. The biases can reach the level of kilometers, and the sign and magnitude are correlate significantly with longitude.

An Orbit Propagation Software for Mars Orbiting Spacecraft

Directory of Open Access Journals (Sweden)

Young-Joo Song

2004-12-01

Full Text Available An orbit propagation software for the Mars orbiting spacecraft has been developed and verified in preparations for the future Korean Mars missions. Dynamic model for Mars orbiting spacecraft has been studied, and Mars centered coordinate systems are utilized to express spacecraft state vectors. Coordinate corrections to the Mars centered coordinate system have been made to adjust the effects caused by Mars precession and nutation. After spacecraft enters Sphere of Influence (SOI of the Mars, the spacecraft experiences various perturbation effects as it approaches to Mars. Every possible perturbation effect is considered during integrations of spacecraft state vectors. The Mars50c gravity field model and the Mars-GRAM 2001 model are used to compute perturbation effects due to Mars gravity field and Mars atmospheric drag, respectively. To compute exact locations of other planets, JPL's DE405 ephemerides are used. Phobos and Deimos's ephemeris are computed using analytical method because their informations are not released with DE405. Mars Global Surveyor's mapping orbital data are used to verify the developed propagator performances. After one Martian day propagation (12 orbital periods, the results show about maximum ±5 meter errors, in every position state components(radial, cross-track and along-track, when compared to these from the Astrogator propagation in the Satellite Tool Kit. This result shows high reliability of the developed software which can be used to design near Mars missions for Korea, in future.

A full-potential linear-muffin-tin-orbital molecular-dynamics study of B{sub 7}, B{sub 10} and B{sub 13} clusters

Energy Technology Data Exchange (ETDEWEB)

Cao Peilin Cao; Zhao Wei; Li Baoxing; Song Bin; Zhou Xuyan [Department of Physics and State Key Laboratory of Silicon Material, Zhejiang University, Hangzhou, Zhejiang (China)

2001-06-04

The structures of B{sub 7}, B{sub 10} and B{sub 13} boron clusters are studied using the full-potential linear-muffin-tin-orbital molecular-dynamics method. Seven stable structures for B{sub 7} and fifteen for B{sub 10} have been obtained. C{sub 2h}-B{sub 10} is the most stable among the 15 structures, but C{sub 2v}-B{sub 10} is not stable. For B{sub 13}, three degenerate ground-state structures have been found. The potential surface near C{sub 2v}-B{sub 7} (ground state) and D{sub 6h}-B{sub 7} is very flat. As a fundamental unit in constructing bigger clusters, C{sub 2v}-B{sub 7} will change its form easily. The most stable structures for B{sub 7}, B{sub 10} and B{sub 13} clusters are two-dimensional (quasi-) planar clusters, rather than the three-dimensional ones. General speaking, these clusters obey the 'Aufbau principle'. (author)

Investigation of naproxen drug using mass spectrometry, thermal analyses and semi-empirical molecular orbital calculation

Directory of Open Access Journals (Sweden)

M.A. Zayed

2017-03-01

Full Text Available Naproxen (C14H14O3 is a non-steroidal anti-inflammatory drug (NSAID. It is important to investigate its structure to know the active groups and weak bonds responsible for medical activity. In the present study, naproxen was investigated by mass spectrometry (MS, thermal analysis (TA measurements (TG/DTG and DTA and confirmed by semi empirical molecular orbital (MO calculation, using PM3 procedure. These calculations included, bond length, bond order, bond strain, partial charge distribution, ionization energy and heat of formation (ΔHf. The mass spectra and thermal analysis fragmentation pathways were proposed and compared to select the most suitable scheme representing the correct fragmentation pathway of the drug in both techniques. The PM3 procedure reveals that the primary cleavage site of the charged molecule is the rupture of the COOH group (lowest bond order and high strain which followed by CH3 loss of the methoxy group. Thermal analysis of the neutral drug reveals a high response to the temperature variation with very fast rate. It decomposed in several sequential steps in the temperature range 80–400 °C. These mass losses appear as two endothermic and one exothermic peaks which required energy values of 255.42, 10.67 and 371.49 J g−1 respectively. The initial thermal ruptures are similar to that obtained by mass spectral fragmentation (COOH rupture. It was followed by the loss of the methyl group and finally by ethylene loss. Therefore, comparison between MS and TA helps in selection of the proper pathway representing its fragmentation. This comparison is successfully confirmed by MO-calculation.

Orbital localization criterion as a complementary tool in the bonding analysis by means of electron localization function: study of the Si(n)(BH)(5-n)(2-) (n = 0-5) clusters.

Science.gov (United States)

Oña, Ofelia B; Alcoba, Diego R; Torre, Alicia; Lain, Luis; Torres-Vega, Juan J; Tiznado, William

2013-12-05

A recently proposed molecular orbital localization procedure, based on the electron localization function (ELF) technique, has been used to describe chemical bonding in the cluster series Sin(BH)(5-n)(2-) (n = 0-5). The method combines the chemically intuitive information obtained from the traditional ELF analysis with the flexibility and generality of canonical molecular orbital theory. This procedure attempts to localize the molecular orbitals in regions that have the highest probability for finding a pair of electrons, providing a chemical bonding description according to the classical Lewis theory. The results confirm that conservation of the structures upon isoelectronic replacement of a B-H group by a Si atom, allowing evolution from B5H5(2-) to Si5(2-), is in total agreement with the preservation of the chemical bonding pattern.

Burn Delay Analysis of the Lunar Orbit Insertion for Korea Pathfinder Lunar Orbiter

Science.gov (United States)

Bae, Jonghee; Song, Young-Joo; Kim, Young-Rok; Kim, Bangyeop

2017-12-01

The first Korea lunar orbiter, Korea Pathfinder Lunar Orbiter (KPLO), has been in development since 2016. After launch, the KPLO will execute several maneuvers to enter into the lunar mission orbit, and will then perform lunar science missions for one year. Among these maneuvers, the lunar orbit insertion (LOI) is the most critical maneuver because the KPLO will experience an extreme velocity change in the presence of the Moon’s gravitational pull. However, the lunar orbiter may have a delayed LOI burn during operation due to hardware limitations and telemetry delays. This delayed burn could occur in different captured lunar orbits; in the worst case, the KPLO could fly away from the Moon. Therefore, in this study, the burn delay for the first LOI maneuver is analyzed to successfully enter the desired lunar orbit. Numerical simulations are performed to evaluate the difference between the desired and delayed lunar orbits due to a burn delay in the LOI maneuver. Based on this analysis, critical factors in the LOI maneuver, the periselene altitude and orbit period, are significantly changed and an additional delta-V in the second LOI maneuver is required as the delay burn interval increases to 10 min from the planned maneuver epoch.

Bonding character and s-p hybridization of orbitals of hydride molecules according to photoelectron spectroscopy data

International Nuclear Information System (INIS)

Vovna, V.I.

1988-01-01

In consideration of the electron structure of the molecules in terms of canonical many-centered orbitals by s-p hybridization we mean mixture of the ns and np orbitals of an atom into one molecular orbital. The PE spectra of the valence levels of the molecules give direct information on the influence of s-p hybridization on the bonding character and energies of the levels [1, 3]. In this article we discuss the influence of hybridization on the bonding character of the MO of the isoelectronic series A 7 H - A 6 H 2 - A 5 H 2 - A 4 H 4 according to the results of PE spectroscopy. To simplify the discussion we adopt the approximation of Kupmans theorem IP i = -var epsilon i

Charge transfer interaction using quasiatomic minimal-basis orbitals in the effective fragment potential method

International Nuclear Information System (INIS)

Xu, Peng; Gordon, Mark S.

2013-01-01

The charge transfer (CT) interaction, the most time-consuming term in the general effective fragment potential method, is made much more computationally efficient. This is accomplished by the projection of the quasiatomic minimal-basis-set orbitals (QUAMBOs) as the atomic basis onto the self-consistent field virtual molecular orbital (MO) space to select a subspace of the full virtual space called the valence virtual space. The diagonalization of the Fock matrix in terms of QUAMBOs recovers the canonical occupied orbitals and, more importantly, gives rise to the valence virtual orbitals (VVOs). The CT energies obtained using VVOs are generally as accurate as those obtained with the full virtual space canonical MOs because the QUAMBOs span the valence part of the virtual space, which can generally be regarded as “chemically important.” The number of QUAMBOs is the same as the number of minimal-basis MOs of a molecule. Therefore, the number of VVOs is significantly smaller than the number of canonical virtual MOs, especially for large atomic basis sets. This leads to a dramatic decrease in the computational cost

GLONASS Orbits in Teqc: Methodology and Future Extension for Using SP3 Orbits

Science.gov (United States)

Estey, L.; Wier, S.

2011-12-01

UNAVCO's teqc software package provides translation of a wide variety of GNSS receiver formats, metadata editing (either during translation to RINEX or on existing RINEX files), time-windowing and epoch decimation editing, and quality check (qc) analysis. Teqc is used extensively in GNSS pre-processing, and is designed to handle mixed satellite constellations, such as GPS, GLONASS, Galileo, and SBAS. The latest release of teqc adds GLONASS orbit calculations using GLONASS broadcast navigation messages, read from RINEX file format, during qc. The ephemerides for each GLONASS SV have time and orbit position in Earth-centered, Earth-fixed x, y, and z coordinates. Following Schenewerk [2003], we use trigonometric interpolation, essentially a fit of a partial sum of the Fourier series for each time-varying cartesian orbital component, allowing estimates of orbit positions at most GLONASS observation times. Tests show the interpolated GLONASS orbits made from the broadcast messages diverge from final orbits little more than the same differences using GPS orbits computed from their broadcast messages. Since GLONASS ephemerides do not use Keplerian orbital elements, GLONASS SV orbits can only be interpolated using this method for time intervals when an adequate sequence of ephemerides are available. For typical daily navigation messages collected at a single sit, when a GLONASS SV is in view less than three hours, that SV's signals are generally not used by teqc due to less precise orbit positions. Teqc quality control including SV position can now use GPS alone, GLONASS alone, or the joint solution. Future work will extend teqc to use SP3 format files, such as the IGS final orbit files, and SBAS data, which have broadcast ephemerides with elements similar to GLONASS.

Spin-orbit-induced spin splittings in polar transition metal dichalcogenide monolayers

KAUST Repository

Cheng, Yingchun

2013-06-01

The Rashba effect in quasi two-dimensional materials, such as noble metal surfaces and semiconductor heterostructures, has been investigated extensively, while interest in real two-dimensional systems has just emerged with the discovery of graphene. We present ab initio electronic structure, phonon, and molecular-dynamics calculations to study the structural stability and spin-orbit-induced spin splitting in the transition metal dichalcogenide monolayers MXY (M = Mo, W and X, Y = S, Se, Te). In contrast to the non-polar systems with X = Y, in the polar systems with X ≠ Y the Rashba splitting at the Γ-point for the uppermost valence band is caused by the broken mirror symmetry. An enhancement of the splitting can be achieved by increasing the spin-orbit coupling and/or the potential gradient. © Copyright EPLA, 2013.

Quasi-molecular processes in dense plasmas

International Nuclear Information System (INIS)

Younger, S.M.

1991-01-01

Quasi-molecular phenomena occur in dense plasmas when the interatomic spacing is comparable to the characteristic wavelength of the electrons. If the electronic states are bound, covalent orbitals arise with different excitation energies, radiative rates, and collisional rates than for isolated ions. For continuum electrons, charge localization near transient clusters of nuclei can influence many scattering and transport processes. We identify several novel consequences of quasi-molecular phenomena in plasmas and give a possible explanation of high energy features associated with helium-like emissions lines observed in recent inertial fusion experiments. 7 refs

Nontraumatic orbital roof encephalocele.

Science.gov (United States)

Hoang, Amber; Maugans, Todd; Ngo, Thang; Ikeda, Jamie

2017-02-01

Intraorbital meningoencephaloceles occur most commonly as a complication of traumatic orbital roof fractures. Nontraumatic congenital orbital meningoncephaloceles are very rare, with most secondary to destructive processes affecting the orbit and primary skull defects. Treatment for intraorbital meningoencephaloceles is surgical repair, involving the excision of herniated brain parenchyma and meninges and reconstruction of the osseous defect. Most congenital lesions present in infancy with obvious globe and orbital deformities; we report an orbital meningoencephalocele in a 3-year-old girl who presented with ptosis. Copyright © 2017 American Association for Pediatric Ophthalmology and Strabismus. Published by Elsevier Inc. All rights reserved.

Contamination Examples and Lessons from Low Earth Orbit Experiments and Operational Hardware

Science.gov (United States)

Pippin, Gary; Finckenor, Miria M.

2009-01-01

Flight experiments flown on the Space Shuttle, the International Space Station, Mir, Skylab, and free flyers such as the Long Duration Exposure Facility, the European Retrievable Carrier, and the EFFU, provide multiple opportunities for the investigation of molecular contamination effects. Retrieved hardware from the Solar Maximum Mission satellite, Mir, and the Hubble Space Telescope has also provided the means gaining insight into contamination processes. Images from the above mentioned hardware show contamination effects due to materials processing, hardware storage, pre-flight cleaning, as well as on-orbit events such as outgassing, mechanical failure of hardware in close proximity, impacts from man-made debris, and changes due to natural environment factors.. Contamination effects include significant changes to thermal and electrical properties of thermal control surfaces, optics, and power systems. Data from several flights has been used to develop a rudimentary estimate of asymptotic values for absorptance changes due to long-term solar exposure (4000-6000 Equivalent Sun Hours) of silicone-based molecular contamination deposits of varying thickness. Recommendations and suggestions for processing changes and constraints based on the on-orbit observed results will be presented.

E-Orbit Functions

Directory of Open Access Journals (Sweden)

Jiri Patera

2008-01-01

Full Text Available We review and further develop the theory of $E$-orbit functions. They are functions on the Euclidean space $E_n$ obtained from the multivariate exponential function by symmetrization by means of an even part $W_{e}$ of a Weyl group $W$, corresponding to a Coxeter-Dynkin diagram. Properties of such functions are described. They are closely related to symmetric and antisymmetric orbit functions which are received from exponential functions by symmetrization and antisymmetrization procedure by means of a Weyl group $W$. The $E$-orbit functions, determined by integral parameters, are invariant withrespect to even part $W^{aff}_{e}$ of the affine Weyl group corresponding to $W$. The $E$-orbit functions determine a symmetrized Fourier transform, where these functions serve as a kernel of the transform. They also determine a transform on a finite set of points of the fundamental domain $F^{e}$ of the group $W^{aff}_{e}$ (the discrete $E$-orbit function transform.

Congenital orbital encephalocele, orbital dystopia, and exophthalmos.

Science.gov (United States)

Hwang, Kun; Kim, Han Joon

2012-07-01

We present here an exceedingly rare variant of a nonmidline basal encephalocele of the spheno-orbital type, and this was accompanied with orbital dystopia in a 56-year-old man. On examination, his left eye was located more inferolaterally than his right eye, and the patient said this had been this way since his birth. The protrusion of his left eye was aggravated when he is tired. His naked visual acuity was 0.7/0.3, and the ocular pressure was 14/12 mm Hg. The exophthalmometry was 10/14 to 16 mm. His eyeball motion was not restricted, yet diplopia was present in all directions. The distance from the midline to the medial canthus was 20/15 mm. The distance from the midline to the midpupillary line was 35/22 mm. The vertical dimension of the palpebral fissure was 12/9 mm. The height difference of the upper eyelid margin was 11 mm, and the height difference of the lower eyelid margin was 8 mm. Facial computed tomography and magnetic resonance imaging showed left sphenoid wing hypoplasia and herniation of the left anterior temporal pole and dura mater into the orbit, and this resulted into left exophthalmos and encephalomalacia in the left anterior temporal pole. To the best of our knowledge, our case is the second case of basal encephalocele and orbital dystopia.

Laser-induced blurring of molecular structure information in high harmonic spectroscopy

DEFF Research Database (Denmark)

Risoud, Francois; Leveque, Camille; Labeye, Marie

2017-01-01

High harmonic spectroscopy gives access to molecular structure with Angstrom resolution. Such information is encoded in the destructive interferences occurring between the harmonic emissions from the different parts of the molecule. By solving the time-dependent Schrodinger equation, either....... These findings have important consequences for molecular imaging and orbital tomography using high harmonic spectroscopy....

Measurement of orbital volume by computed tomography. Especially on the growth of orbit

Energy Technology Data Exchange (ETDEWEB)

Furuta, Minoru [Fukushima Medical Coll. (Japan)

2000-10-01

Using reconstructed X-ray computed tomography (CT) images of serial coronal sections, we measured the orbital volume and studied its changes with age. The subjects consisted of 109 patients (74 males, 35 females) who had undergone X-ray CT. After the reproducibility of orbital volume measurements and laterality in individuals were confirmed, the relation between the orbital volume and the age, sex, weight, and interlateral orbital rim distance were examined. The difference between two measurements in the same patients was 0.4% for measured volume, which showed the reproducibility of this measurement to be good. The laterality in individuals was 0.06 cm{sup 3}: this difference was very small and not significant. The orbital volume showed no unbalance between the right and left at any stage of growth. Both the height and the interlateral orbital rim distance had a strong correlation with the orbital volume. Referring to the relation between age and orbital volume, a strong correlation with an almost identical approximate equation was obtained for both sexes under 12 years of age. Presumably, the rapid growth of the orbit comes to an end by 15 years of age in males and 11 years in females. This means that more than 95% growth of adults has already been completed in the first half of the teens. The mean orbital volume in adult Japanese is 23.6{+-}2.0 (mean{+-}standard deviation) cm{sup 3} in males and 20.9{+-}1.3 cm{sup 3} in females. (author)

Measurement of orbital volume by computed tomography. Especially on the growth of orbit

International Nuclear Information System (INIS)

Furuta, Minoru

2000-01-01

Using reconstructed X-ray computed tomography (CT) images of serial coronal sections, we measured the orbital volume and studied its changes with age. The subjects consisted of 109 patients (74 males, 35 females) who had undergone X-ray CT. After the reproducibility of orbital volume measurements and laterality in individuals were confirmed, the relation between the orbital volume and the age, sex, weight, and interlateral orbital rim distance were examined. The difference between two measurements in the same patients was 0.4% for measured volume, which showed the reproducibility of this measurement to be good. The laterality in individuals was 0.06 cm 3 : this difference was very small and not significant. The orbital volume showed no unbalance between the right and left at any stage of growth. Both the height and the interlateral orbital rim distance had a strong correlation with the orbital volume. Referring to the relation between age and orbital volume, a strong correlation with an almost identical approximate equation was obtained for both sexes under 12 years of age. Presumably, the rapid growth of the orbit comes to an end by 15 years of age in males and 11 years in females. This means that more than 95% growth of adults has already been completed in the first half of the teens. The mean orbital volume in adult Japanese is 23.6±2.0 (mean±standard deviation) cm 3 in males and 20.9±1.3 cm 3 in females. (author)

Low-Cost 3D Printing Orbital Implant Templates in Secondary Orbital Reconstructions.

Science.gov (United States)

Callahan, Alison B; Campbell, Ashley A; Petris, Carisa; Kazim, Michael

Despite its increasing use in craniofacial reconstructions, three-dimensional (3D) printing of customized orbital implants has not been widely adopted. Limitations include the cost of 3D printers able to print in a biocompatible material suitable for implantation in the orbit and the breadth of available implant materials. The authors report the technique of low-cost 3D printing of orbital implant templates used in complex, often secondary, orbital reconstructions. A retrospective case series of 5 orbital reconstructions utilizing a technique of 3D printed orbital implant templates is presented. Each patient's Digital Imaging and Communications in Medicine data were uploaded and processed to create 3D renderings upon which a customized implant was designed and sent electronically to printers open for student use at our affiliated institutions. The mock implants were sterilized and used intraoperatively as a stencil and mold. The final implant material was chosen by the surgeons based on the requirements of the case. Five orbital reconstructions were performed with this technique: 3 tumor reconstructions and 2 orbital fractures. Four of the 5 cases were secondary reconstructions. Molded Medpor Titan (Stryker, Kalamazoo, MI) implants were used in 4 cases and titanium mesh in 1 case. The stenciled and molded implants were adjusted no more than 2 times before anchored in place (mean 1). No case underwent further revision. The technique and cases presented demonstrate 1) the feasibility and accessibility of low-cost, independent use of 3D printing technology to fashion patient-specific implants in orbital reconstructions, 2) the ability to apply this technology to the surgeon's preference of any routinely implantable material, and 3) the utility of this technique in complex, secondary reconstructions.

Stable low-altitude orbits around Ganymede considering a disturbing body in a circular orbit

Science.gov (United States)

Cardoso dos Santos, J.; Carvalho, J. P. S.; Vilhena de Moraes, R.

2014-10-01

Some missions are being planned to visit Ganymede like the Europa Jupiter System Mission that is a cooperation between NASA and ESA to insert the spacecraft JGO (Jupiter Ganymede Orbiter) into Ganymedes orbit. This comprehension of the dynamics of these orbits around this planetary satellite is essential for the success of this type of mission. Thus, this work aims to perform a search for low-altitude orbits around Ganymede. An emphasis is given in polar orbits and it can be useful in the planning of space missions to be conducted around, with respect to the stability of orbits of artificial satellites. The study considers orbits of artificial satellites around Ganymede under the influence of the third-body (Jupiter's gravitational attraction) and the polygenic perturbations like those due to non-uniform distribution of mass (J_2 and J_3) of the main body. A simplified dynamic model for these perturbations is used. The Lagrange planetary equations are used to describe the orbital motion of the artificial satellite. The equations of motion are developed in closed form to avoid expansions in eccentricity and inclination. The results show the argument of pericenter circulating. However, low-altitude (100 and 150 km) polar orbits are stable. Another orbital elements behaved variating with small amplitudes. Thus, such orbits are convenient to be applied to future space missions to Ganymede. Acknowledgments: FAPESP (processes n° 2011/05671-5, 2012/12539-9 and 2012/21023-6).

Titan Orbiter Aerorover Mission

Science.gov (United States)

Sittler Jr., E. C.; Acuna, M.; Burchell, M. J.; Coates, A.; Farrell, W.; Flasar, M.; Goldstein, B. E.; Gorevan, S.; Hartle, R. E.; Johnson, W. T. K.

2001-01-01

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.

Harmonically excited orbital variations

International Nuclear Information System (INIS)

Morgan, T.

1985-01-01

Rephrasing the equations of motion for orbital maneuvers in terms of Lagrangian generalized coordinates instead of Newtonian rectangular cartesian coordinates can make certain harmonic terms in the orbital angular momentum vector more readily apparent. In this formulation the equations of motion adopt the form of a damped harmonic oscillator when torques are applied to the orbit in a variationally prescribed manner. The frequencies of the oscillator equation are in some ways unexpected but can nonetheless be exploited through resonant forcing functions to achieve large secular variations in the orbital elements. Two cases are discussed using a circular orbit as the control case: (1) large changes in orbital inclination achieved by harmonic excitation rather than one impulsive velocity change, and (2) periodic and secular changes to the longitude of the ascending node using both stable and unstable excitation strategies. The implications of these equations are also discussed for both artificial satellites and natural satellites. For the former, two utilitarian orbits are suggested, each exploiting a form of harmonic excitation. 5 refs

Dynamic and reduced-dynamic precise orbit determination of satellites in low earth orbits

International Nuclear Information System (INIS)

Swatschina, P.

2009-01-01

The precise positioning of satellites in Low Earth Orbits (LEO) has become a key technology for advanced space missions. Dedicated satellite missions, such as CHAMP, GRACE and GOCE, that aim to map the Earths gravity field and its variation over time with unprecedented accuracy, initiated the demand for highly precise orbit solutions of LEO satellites. Furthermore, a wide range of additional science opportunities opens up with the capability to generate accurate LEO orbits. For all considered satellite missions, the primary measurement system for navigation is a spaceborne GPS receiver. The goal of this thesis is to establish and implement methods for Precise Orbit Determination (POD) of LEO satellites using GPS. Striving for highest precision using yet efficient orbit generation strategies, the attained orbit solutions are aimed to be competitive with the most advanced solutions of other institutions. Dynamic and reduced-dynamic orbit models provide the basic concepts of this work. These orbit models are subsequently adjusted to the highly accurate GPS measurements. The GPS measurements are introduced at the zero difference level in the ionosphere free linear combination. Appropriate procedures for GPS data screening and editing are established to detect erroneous data and to employ measurements of good quality only. For the dynamic orbit model a sophisticated force model, especially designed for LEO satellites, has been developed. In order to overcome the limitations that are induced by the deficiencies of the purely dynamical model, two different types of empirical parameters are introduced into the force model. These reduced-dynamic orbit models allow for the generation of much longer orbital arcs while preserving the spacecraft dynamics to the most possible extent. The two methods for reduced-dynamic orbit modeling are instantaneous velocity changes (pulses) or piecewise constant accelerations. For both techniques highly efficient modeling algorithms are

Spin-orbit torques from interfacial spin-orbit coupling for various interfaces

Science.gov (United States)

Kim, Kyoung-Whan; Lee, Kyung-Jin; Sinova, Jairo; Lee, Hyun-Woo; Stiles, M. D.

2017-09-01

We use a perturbative approach to study the effects of interfacial spin-orbit coupling in magnetic multilayers by treating the two-dimensional Rashba model in a fully three-dimensional description of electron transport near an interface. This formalism provides a compact analytic expression for current-induced spin-orbit torques in terms of unperturbed scattering coefficients, allowing computation of spin-orbit torques for various contexts, by simply substituting scattering coefficients into the formulas. It applies to calculations of spin-orbit torques for magnetic bilayers with bulk magnetism, those with interface magnetism, a normal-metal/ferromagnetic insulator junction, and a topological insulator/ferromagnet junction. It predicts a dampinglike component of spin-orbit torque that is distinct from any intrinsic contribution or those that arise from particular spin relaxation mechanisms. We discuss the effects of proximity-induced magnetism and insertion of an additional layer and provide formulas for in-plane current, which is induced by a perpendicular bias, anisotropic magnetoresistance, and spin memory loss in the same formalism.

Orbit-attitude coupled motion around small bodies: Sun-synchronous orbits with Sun-tracking attitude motion

Science.gov (United States)

Kikuchi, Shota; Howell, Kathleen C.; Tsuda, Yuichi; Kawaguchi, Jun'ichiro

2017-11-01

The motion of a spacecraft in proximity to a small body is significantly perturbed due to its irregular gravity field and solar radiation pressure. In such a strongly perturbed environment, the coupling effect of the orbital and attitude motions exerts a large influence that cannot be neglected. However, natural orbit-attitude coupled dynamics around small bodies that are stationary in both orbital and attitude motions have yet to be observed. The present study therefore investigates natural coupled motion that involves both a Sun-synchronous orbit and Sun-tracking attitude motion. This orbit-attitude coupled motion enables a spacecraft to maintain its orbital geometry and attitude state with respect to the Sun without requiring active control. Therefore, the proposed method can reduce the use of an orbit and attitude control system. This paper first presents analytical conditions to achieve Sun-synchronous orbits and Sun-tracking attitude motion. These analytical solutions are then numerically propagated based on non-linear coupled orbit-attitude equations of motion. Consequently, the possibility of implementing Sun-synchronous orbits with Sun-tracking attitude motion is demonstrated.

Study on different influence of pyrimidine and phenyl on current-voltage characteristics of molecular devices

International Nuclear Information System (INIS)

Fu Xiaoxiao; Li Zongliang

2011-01-01

By using ab initio method and elastic scattering Green's function theory, electronic transport properties of symmetric tetraphenyl and non-symmetric diblock dipyrimidinyldiphenyl molecules are investigated. The numerical results show that, the tetraphenyl molecule has better electronic conductivity than the diblock molecule. The diblock molecule exhibits pronounced rectification behavior. Some molecular orbitals of the tetraphenyl molecule are delocalized into the two gold electrodes simultaneously which results in the better electronic conductivity. However, the non-symmetric structure of diblock molecule leads to the localization of the molecular orbitals, which is a disadvantage to the electronic transport. (authors)

Electron Interference in Molecular Circular Polarization Attosecond XUV Photoionization

Directory of Open Access Journals (Sweden)

Kai-Jun Yuan

2015-01-01

Full Text Available Two-center electron interference in molecular attosecond photoionization processes is investigated from numerical solutions of time-dependent Schrödinger equations. Both symmetric H\\(_2^+\\ and nonsymmetric HHe\\(^{2+}\\ one electron diatomic systems are ionized by intense attosecond circularly polarized XUV laser pulses. Photoionization of these molecular ions shows signature of interference with double peaks (minima in molecular attosecond photoelectron energy spectra (MAPES at critical angles \\(\\vartheta_c\\ between the molecular \\(\\textbf{R}\\ axis and the photoelectron momentum \\(\\textbf{p}\\. The interferences are shown to be a function of the symmetry of electronic states and the interference patterns are sensitive to the molecular orientation and pulse polarization. Such sensitivity offers possibility for imaging of molecular structure and orbitals.

Two dimensional molecular electronics spectroscopy for molecular fingerprinting, DNA sequencing, and cancerous DNA recognition.

Science.gov (United States)

Rajan, Arunkumar Chitteth; Rezapour, Mohammad Reza; Yun, Jeonghun; Cho, Yeonchoo; Cho, Woo Jong; Min, Seung Kyu; Lee, Geunsik; Kim, Kwang S

2014-02-25

Laser-driven molecular spectroscopy of low spatial resolution is widely used, while electronic current-driven molecular spectroscopy of atomic scale resolution has been limited because currents provide only minimal information. However, electron transmission of a graphene nanoribbon on which a molecule is adsorbed shows molecular fingerprints of Fano resonances, i.e., characteristic features of frontier orbitals and conformations of physisorbed molecules. Utilizing these resonance profiles, here we demonstrate two-dimensional molecular electronics spectroscopy (2D MES). The differential conductance with respect to bias and gate voltages not only distinguishes different types of nucleobases for DNA sequencing but also recognizes methylated nucleobases which could be related to cancerous cell growth. This 2D MES could open an exciting field to recognize single molecule signatures at atomic resolution. The advantages of the 2D MES over the one-dimensional (1D) current analysis can be comparable to those of 2D NMR over 1D NMR analysis.

Linear Discriminant Analysis for the in Silico Discovery of Mechanism-Based Reversible Covalent Inhibitors of a Serine Protease: Application of Hydration Thermodynamics Analysis and Semi-empirical Molecular Orbital Calculation.

Science.gov (United States)

Masuda, Yosuke; Yoshida, Tomoki; Yamaotsu, Noriyuki; Hirono, Shuichi

2018-01-01

We recently reported that the Gibbs free energy of hydrolytic water molecules (ΔG wat ) in acyl-trypsin intermediates calculated by hydration thermodynamics analysis could be a useful metric for estimating the catalytic rate constants (k cat ) of mechanism-based reversible covalent inhibitors. For thorough evaluation, the proposed method was tested with an increased number of covalent ligands that have no corresponding crystal structures. After modeling acyl-trypsin intermediate structures using flexible molecular superposition, ΔG wat values were calculated according to the proposed method. The orbital energies of antibonding π* molecular orbitals (MOs) of carbonyl C=O in covalently modified catalytic serine (E orb ) were also calculated by semi-empirical MO calculations. Then, linear discriminant analysis (LDA) was performed to build a model that can discriminate covalent inhibitor candidates from substrate-like ligands using ΔG wat and E orb . The model was built using a training set (10 compounds) and then validated by a test set (4 compounds). As a result, the training set and test set ligands were perfectly discriminated by the model. Hydrolysis was slower when (1) the hydrolytic water molecule has lower ΔG wat ; (2) the covalent ligand presents higher E orb (higher reaction barrier). Results also showed that the entropic term of hydrolytic water molecule (-TΔS wat ) could be used for estimating k cat and for covalent inhibitor optimization; when the rotational freedom of the hydrolytic water molecule is limited, the chance for favorable interaction with the electrophilic acyl group would also be limited. The method proposed in this study would be useful for screening and optimizing the mechanism-based reversible covalent inhibitors.

Modeling of Salt Solubilities in Mixed Solvents

DEFF Research Database (Denmark)

Chiavone-Filho, O.; Rasmussen, Peter

2000-01-01

A method to correlate and predict salt solubilities in mixed solvents using a UNIQUAC+Debye-Huckel model is developed. The UNIQUAC equation is applied in a form with temperature-dependent parameters. The Debye-Huckel model is extended to mixed solvents by properly evaluating the dielectric...... constants and the liquid densities of the solvent media. To normalize the activity coefficients, the symmetric convention is adopted. Thermochemical properties of the salt are used to estimate the solubility product. It is shown that the proposed procedure can describe with good accuracy a series of salt...

Congenital orbital teratoma

OpenAIRE

Aiyub, Shereen; Chan, Weng Onn; Szetu, John; Sullivan, Laurence J; Pater, John; Cooper, Peter; Selva, Dinesh

2013-01-01

We present a case of mature congenital orbital teratoma managed with lid-sparing exenteration and dermis fat graft. This is a case report on the management of congenital orbital teratoma. A full-term baby was born in Fiji with prolapsed right globe which was surrounded by a nonpulsatile, cystic mass. Clinical and imaging features were consistent with congenital orbital teratoma. Due to limited surgical expertise, the patient was transferred to Adelaide, Australia for further management. The p...

Investigation of electron momentum distributions for outer valence orbitals of trichlorofluoromethane by (e, 2e) electron momentum spectroscopy

International Nuclear Information System (INIS)

Zhou, L.X.; Shan, X.; Chen, X.J.; Yin, X.F.; Zhang, X.H.; Xu, C.K.; Wei, Z.; Xu, K.Z.

2006-01-01

The binding energy spectra and electron momentum distributions for the outer valence orbitals of trichlorofluoromethane (CFCl 3 ) have been measured by binary (e, 2e) electron momentum spectroscopy (EMS) at an impact energy of 1200 eV + binding energy. The experimental electron momentum profiles are compared with Hartree-Fock and density functional theory (DFT) calculations with different-sized basis sets. Generally, the DFT calculations employing B3LYP functional with large basis sets of AUG-cc-pVDZ and AUG-cc-pVTZ give better description of the experimental results. But for 3e orbital, all the theoretical calculations underestimate the experiment, which is probably due to the distorted-wave effect that often occurs in π*-like molecular orbital

Density functional theory studies on the structures and electronic communication of meso-ferrocenylporphyrins: long range orbital coupling via porphyrin core.

Science.gov (United States)

Zhang, Lijuan; Qi, Dongdong; Zhang, Yuexing; Bian, Yongzhong; Jiang, Jianzhuang

2011-02-01

The molecular and electronic structures together with the electronic absorption spectra of a series of metal free meso-ferrocenylporphyrins, namely 5-ferrocenylporphyrin (1), 5,10-diferrocenylporphyrin (2), 5,15-diferrocenylporphyrin (3), 5,10,15-triferrocenylporphyrin (4), and 5,10,15,20-tetraferrocenylporphyrin (5) have been studied with the density functional theory (DFT) and time-dependent density functional theory (TD-DFT) methods. For the purpose of comparative studies, metal free porphyrin without any ferrocenyl group (0) and isolated ferrocene (6) were also calculated. The effects of the number and position of meso-attached ferrocenyl substituents on their molecular and electronic structures, atomic charges, molecular orbitals, and electronic absorption spectra of 1-5 were systematically investigated. The orbital coupling is investigated in detail, explaining well the long range coupling of ferrocenyl substituents connected via porphyrin core and the systematic change in the electronic absorption spectra of porphyrin compounds. Copyright © 2010 Elsevier Inc. All rights reserved.

Topology of tokamak orbits

International Nuclear Information System (INIS)

Rome, J.A.; Peng, Y.K.M.

1978-09-01

Guiding center orbits in noncircular axisymmetric tokamak plasmas are studied in the constants of motion (COM) space of (v, zeta, psi/sub m/). Here, v is the particle speed, zeta is the pitch angle with respect to the parallel equilibrium current, J/sub parallels/, and psi/sub m/ is the maximum value of the poloidal flux function (increasing from the magnetic axis) along the guiding center orbit. Two D-shaped equilibria in a flux-conserving tokamak having β's of 1.3% and 7.7% are used as examples. In this space, each confined orbit corresponds to one and only one point and different types of orbits (e.g., circulating, trapped, stagnation and pinch orbits) are represented by separate regions or surfaces in the space. It is also shown that the existence of an absolute minimum B in the higher β (7.7%) equilibrium results in a dramatically different orbit topology from that of the lower β case. The differences indicate the confinement of additional high energy (v → c, within the guiding center approximation) trapped, co- and countercirculating particles whose orbit psi/sub m/ falls within the absolute B well

Ab initio Molecular Orbital Studies of the Vibrational Spectra of some ...

African Journals Online (AJOL)

NJD

2004-06-15

Jun 15, 2004 ... molecular complexes containing the family of Lewis acids carbon dioxide ..... cating a successively weaker interaction along the series. For. SO2. ..... Schleyer, H.F. Schaefer III, P.R. Scheiner, W.L. Jorgensen, W. Thiel and.

Molecular selectivity of graphene-enhanced Raman scattering.

Science.gov (United States)

Huang, Shengxi; Ling, Xi; Liang, Liangbo; Song, Yi; Fang, Wenjing; Zhang, Jin; Kong, Jing; Meunier, Vincent; Dresselhaus, Mildred S

2015-05-13

Graphene-enhanced Raman scattering (GERS) is a recently discovered Raman enhancement phenomenon that uses graphene as the substrate for Raman enhancement and can produce clean and reproducible Raman signals of molecules with increased signal intensity. Compared to conventional Raman enhancement techniques, such as surface-enhanced Raman scattering (SERS) and tip-enhanced Raman scattering (TERS), in which the Raman enhancement is essentially due to the electromagnetic mechanism, GERS mainly relies on a chemical mechanism and therefore shows unique molecular selectivity. In this paper, we report graphene-enhanced Raman scattering of a variety of different molecules with different molecular properties. We report a strong molecular selectivity for the GERS effect with enhancement factors varying by as much as 2 orders of magnitude for different molecules. Selection rules are discussed with reference to two main features of the molecule, namely its molecular energy levels and molecular structures. In particular, the enhancement factor involving molecular energy levels requires the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies to be within a suitable range with respect to graphene's Fermi level, and this enhancement effect can be explained by the time-dependent perturbation theory of Raman scattering. The enhancement factor involving the choice of molecular structures indicates that molecular symmetry and substituents similar to that of the graphene structure are found to be favorable for GERS enhancement. The effectiveness of these factors can be explained by group theory and the charge-transfer interaction between molecules and graphene. Both factors, involving the molecular energy levels and structural symmetry of the molecules, suggest that a remarkable GERS enhancement requires strong molecule-graphene coupling and thus effective charge transfer between the molecules and graphene. These conclusions are further

Correlation between the 2-Dimensional Extent of Orbital Defects and the 3-Dimensional Volume of Herniated Orbital Content in Patients with Isolated Orbital Wall Fractures

Directory of Open Access Journals (Sweden)

Jong Hyun Cha

2017-01-01

Full Text Available BackgroundThe purpose of this study was to assess the correlation between the 2-dimensional (2D extent of orbital defects and the 3-dimensional (3D volume of herniated orbital content in patients with an orbital wall fracture.MethodsThis retrospective study was based on the medical records and radiologic data of 60 patients from January 2014 to June 2016 for a unilateral isolated orbital wall fracture. They were classified into 2 groups depending on whether the fracture involved the inferior wall (group I, n=30 or the medial wall (group M, n=30. The 2D area of the orbital defect was calculated using the conventional formula. The 2D extent of the orbital defect and the 3D volume of herniated orbital content were measured with 3D image processing software. Statistical analysis was performed to evaluate the correlations between the 2D and 3D parameters.ResultsVarying degrees of positive correlation were found between the 2D extent of the orbital defects and the 3D herniated orbital volume in both groups (Pearson correlation coefficient, 0.568−0.788; R2=32.2%−62.1%.ConclusionsBoth the calculated and measured 2D extent of the orbital defects showed a positive correlation with the 3D herniated orbital volume in orbital wall fractures. However, a relatively large volume of herniation (>0.9 cm3 occurred not infrequently despite the presence of a small orbital defect (<1.9 cm2. Therefore, estimating the 3D volume of the herniated content in addition to the 2D orbital defect would be helpful for determining whether surgery is indicated and ensuring adequate surgical outcomes.

Studies of the electron density in the highest occupied molecular orbitals of PH 3, PF 3 and P(CH 3) 3 by electron momentum spectroscopy and Hartree-Fock, MRSD-CI and DFT calculations

Science.gov (United States)

Rolke, J.; Brion, C. E.

1996-06-01

The spherically averaged momentum profiles for the highest occupied molecular orbitals of PF 3 and P(CH 3) 3 have been obtained by electron momentum spectroscopy. The measurements provide a stringent test of basis set effects and the quality of ab-initio methods in the description of these larger molecular systems. As in previous work on the methyl-substituted amines, intuitive arguments fail to predict the correct amount of s- and p-type contributions to the momentum profile while delocalized molecular orbital concepts provide a more adequate description of the HOMOs. The experimental momentum profiles have been compared with theoretical momentum profiles calculated at the level of the target Hartree-Fock approximation with a range of basis sets. New Hartree-Fock calculations are also presented for the HOMO of PH 3 and compared to previously published experimental and theoretical momentum profiles. The experimental momentum profiles have further been compared to calculations at the level of the target Kohn-Sham approximation using density functional theory with the local density approximation and also with gradient corrected (non-local) exchange correlation potentials. In addition, total energies and dipole moments have been calculated for all three molecules by the various theoretical methods and compared to experimental values. Calculated 'density difference maps' show the regions where the HOMO momentum and position electron densities of PF 3 and P(CH 3) 3 change relative to the corresponding HOMO density of PH 3. The results suggest that methyl groups have an electron-attracting effect (relative to H) on the HOMO charge density in trimethyl phosphines. These conclusions are supported by a consideration of dipole moments and the 31P NMR chemical shifts for PH 3, PF 3 and P(CH 3) 3.

Neonatal orbital abscess

Directory of Open Access Journals (Sweden)

Khalil M Al-Salem

2014-01-01

Full Text Available Orbital complications due to ethmoiditis are rare in neonates. A case of orbital abscess due to acute ethmoiditis in a 28-day-old girl is presented. A Successful outcome was achieved following antimicrobial therapy alone; spontaneous drainage of the abscess occurred from the lower lid without the need for surgery. From this case report, we intend to emphasize on eyelid retraction as a sign of neonatal orbital abscess, and to review all the available literature of similar cases.

Orbital-Optimized MP3 and MP2.5 with Density-Fitting and Cholesky Decomposition Approximations.

Science.gov (United States)

Bozkaya, Uğur

2016-03-08

Efficient implementations of the orbital-optimized MP3 and MP2.5 methods with the density-fitting (DF-OMP3 and DF-OMP2.5) and Cholesky decomposition (CD-OMP3 and CD-OMP2.5) approaches are presented. The DF/CD-OMP3 and DF/CD-OMP2.5 methods are applied to a set of alkanes to compare the computational cost with the conventional orbital-optimized MP3 (OMP3) [Bozkaya J. Chem. Phys. 2011, 135, 224103] and the orbital-optimized MP2.5 (OMP2.5) [Bozkaya and Sherrill J. Chem. Phys. 2014, 141, 204105]. Our results demonstrate that the DF-OMP3 and DF-OMP2.5 methods provide considerably lower computational costs than OMP3 and OMP2.5. Further application results show that the orbital-optimized methods are very helpful for the study of open-shell noncovalent interactions, aromatic bond dissociation energies, and hydrogen transfer reactions. We conclude that the DF-OMP3 and DF-OMP2.5 methods are very promising for molecular systems with challenging electronic structures.

Application of the Fenske-Hall molecular orbital method to the calculation of 11B NMR chemical shifts. Antipodal substituent effects in deltahedral clusters

International Nuclear Information System (INIS)

Fehlner, T.P.; Czech, P.T.; Fenske, R.F.

1990-01-01

Utilizing Fenske-Hall wave functions and eigenvalues combined with the Ramsey sum over states (SOS) approximation, it is demonstrated that the sign and magnitude of the paramagnetic contribution to the shielding correlates well with the observed 11 B chemical shifts of a substantial variety of boron- and metal-containing compounds. Analysis of the molecular orbital (MO) contributions in the SOS approximation leads to an explanation of the large downfield shifts associated with metal-rich metallaboranes. A similar analysis demonstrates the importance of selected cluster occupied and unoccupied MO's in explaining both exo-cage substituent effects in which the antipodal boron resonance is shifted upfield and endo-cage substituent effects (interchange of isolobal fragments within the cage framework) in which the antipodal boron resonance is shifted downfield. Exo- and endo-cage substitution perturbs these MO's in an understandable fashion, leading to an internally consistent explanation of the observed chemical shift changes. 36 refs., 8 figs., 4 tabs

Analysis of spin-Hamiltonian and molecular orbital coefficients of Cu2+ doped C8H11KO8 single crystal through EPR technique

Science.gov (United States)

Juliet sheela, K.; Krishnan, S. Radha; Shanmugam, V. M.; Subramanian, P.

2018-04-01

Electron paramagnetic resonance (EPR) studies have been investigated at X-band microwave frequency on Cu2+ ion incorporated into the single crystal of potassium succinate-succinic acid (KSSA) at room temperature. The angular variation of the EPR spectra has shown two magnetically in-equivalent Cu2+ sites in the KSSA single crystal system. The spin Hamiltonian parameters g and A are determined which reveals that the site I and site II occupied in rhombic and axial local field symmetry around the impurity ion. Among the two paramagnetic impurity ions, sites one occupies at substituitional position in the place of monovalent cation (K+) in the crystal whereas the other enters in its lattice interstitially by the correlation of EPR and crystal structure data. From the calculated principle values gxx, gyy, gzz and Axx, Ayy, Azz of both the sites, the admixture coefficients and molecular orbital coefficients were evaluated which gives the information of ground state wave function and types of bonding of impurity ions with the ligands.

Research for molecular magnetic theory

International Nuclear Information System (INIS)

Kuang Xiaoyu; Zhou Kangwei; Gou Qingquan

2002-01-01

Recently, the authors have established a DSF theoretical method suitable for researching molecular magnetism of the compounds consisting of transition group elements. By this method, the authors have revealed that the ferromagnetism of molecules is due to the cross-interaction between d orbitals of adjacent transition-metal ions, and that the antiferromagnetism is due to the parallel interactions. Further more, the authors have also established a magnetism theory for hetero-dinuclear molecular systems and covalent molecular systems, respectively. With these theoretical methods, a systematical studies are performed for the magnetism origin and the magnetism variation rule of transition metal complex molecules in various inorganic compounds, organic compounds and biologic proteins, and a reasonable explanation is presented for the strong antiferromagnetic coupling phenomenon in the catalysis active center of ribonucleotide reductase. This indicates that the main physical mechanisms are the combined effect of the direct-exchange, kinetic exchange and the molecular covalent property

Maintaining Aura's Orbit Requirements While Performing Orbit Maintenance Maneuvers Containing an Orbit Normal Delta-V Component

Science.gov (United States)

Johnson, Megan R.; Petersen, Jeremy D.

2014-01-01

The Earth Observing System (EOS) Afternoon Constellation consists of five member missions (GCOM-W1, Aqua, CALIPSO, CloudSat, and Aura), each of which maintain a frozen, sun-synchronous orbit with a 16-day repeating ground track that follows the Worldwide Reference System-2 (WRS-2). Under nominal science operations for Aura, the propulsion system is oriented such that the resultant thrust vector is aligned 13.493 degrees away from the velocity vector along the yaw axis. When performing orbit maintenance maneuvers, the spacecraft performs a yaw slew to align the thrust vector in the appropriate direction. A new Drag Make Up (DMU) maneuver operations scheme has been implemented for Aura alleviating the need for the 13.493 degree yaw slew. The focus of this investigation is to assess the impact that no-slew DMU maneuver operations will have on Aura's Mean Local Time (MLT) which drives the required along track separation between Aura and the constellation members, as well as Aura's frozen orbit properties, eccentricity and argument of perigee. Seven maneuver strategies were analyzed to determine the best operational approach. A mirror pole strategy, with maneuvers alternating at the North and South poles, was implemented operationally to minimize impact to the MLT. Additional analysis determined that the mirror pole strategy could be further modified to include frozen orbit maneuvers and thus maintain both MLT and the frozen orbit properties under noslew operations.

Update on orbital reconstruction.

Science.gov (United States)

Chen, Chien-Tzung; Chen, Yu-Ray

2010-08-01

Orbital trauma is common and frequently complicated by ocular injuries. The recent literature on orbital fracture is analyzed with emphasis on epidemiological data assessment, surgical timing, method of approach and reconstruction materials. Computed tomographic (CT) scan has become a routine evaluation tool for orbital trauma, and mobile CT can be applied intraoperatively if necessary. Concomitant serious ocular injury should be carefully evaluated preoperatively. Patients presenting with nonresolving oculocardiac reflex, 'white-eyed' blowout fracture, or diplopia with a positive forced duction test and CT evidence of orbital tissue entrapment require early surgical repair. Otherwise, enophthalmos can be corrected by late surgery with a similar outcome to early surgery. The use of an endoscope-assisted approach for orbital reconstruction continues to grow, offering an alternative method. Advances in alloplastic materials have improved surgical outcome and shortened operating time. In this review of modern orbital reconstruction, several controversial issues such as surgical indication, surgical timing, method of approach and choice of reconstruction material are discussed. Preoperative fine-cut CT image and thorough ophthalmologic examination are key elements to determine surgical indications. The choice of surgical approach and reconstruction materials much depends on the surgeon's experience and the reconstruction area. Prefabricated alloplastic implants together with image software and stereolithographic models are significant advances that help to more accurately reconstruct the traumatized orbit. The recent evolution of orbit reconstruction improves functional and aesthetic results and minimizes surgical complications.

Satellite laser ranging to low Earth orbiters: orbit and network validation

Science.gov (United States)

Arnold, Daniel; Montenbruck, Oliver; Hackel, Stefan; Sośnica, Krzysztof

2018-04-01

Satellite laser ranging (SLR) to low Earth orbiters (LEOs) provides optical distance measurements with mm-to-cm-level precision. SLR residuals, i.e., differences between measured and modeled ranges, serve as a common figure of merit for the quality assessment of orbits derived by radiometric tracking techniques. We discuss relevant processing standards for the modeling of SLR observations and highlight the importance of line-of-sight-dependent range corrections for the various types of laser retroreflector arrays. A 1-3 cm consistency of SLR observations and GPS-based precise orbits is demonstrated for a wide range of past and present LEO missions supported by the International Laser Ranging Service (ILRS). A parameter estimation approach is presented to investigate systematic orbit errors and it is shown that SLR validation of LEO satellites is not only able to detect radial but also along-track and cross-track offsets. SLR residual statistics clearly depend on the employed precise orbit determination technique (kinematic vs. reduced-dynamic, float vs. fixed ambiguities) but also reveal pronounced differences in the ILRS station performance. Using the residual-based parameter estimation approach, corrections to ILRS station coordinates, range biases, and timing offsets are derived. As a result, root-mean-square residuals of 5-10 mm have been achieved over a 1-year data arc in 2016 using observations from a subset of high-performance stations and ambiguity-fixed orbits of four LEO missions. As a final contribution, we demonstrate that SLR can not only validate single-satellite orbit solutions but also precise baseline solutions of formation flying missions such as GRACE, TanDEM-X, and Swarm.

Quantifying the Sigma and Pi interactions between U(V) f orbitals and halide, alkyl, alkoxide, amide and ketimide ligands

Energy Technology Data Exchange (ETDEWEB)

University of California, Berkeley; Lukens, Wayne W.; Edelstein, Norman M.; Magnani, Nicola; Hayton, Trevor W.; Fortier, Skye; Seaman, Lani A.

2013-06-20

f Orbital bonding in actinide and lanthanide complexes is critical to their behavior in a variety of areas from separations to magnetic properties. Octahedral f1 hexahalide complexes have been extensively used to study f orbital bonding due to their simple electronic structure and extensive spectroscopic characterization. The recent expansion of this family to include alkyl, alkoxide, amide, and ketimide ligands presents the opportunity to extend this study to a wider variety of ligands. To better understand f orbital bonding in these complexes, the existing molecular orbital (MO) model was refined to include the effect of covalency on spin orbit coupling in addition to its effect on orbital angular momentum (orbital reduction). The new MO model as well as the existing MO model and the crystal field (CF) model were applied to the octahedral f1 complexes to determine the covalency and strengths of the ? and ? bonds formed by the f orbitals. When covalency is significant, MO models more precisely determined the strengths of the bonds derived from the f orbitals; however, when covalency was small, the CF model was better than either MO model. The covalency determined using the new MO model is in better agreement with both experiment and theory than that predicted by the existing MO model. The results emphasize the role played by the orbital energy in determining the strength and covalency of bonds formed by the f orbitals.

Orbital glass in HTSC

International Nuclear Information System (INIS)

Kusmartsev, F.V.

1992-10-01

The physical reasons why the orbital glass may exist in granular high-temperature superconductors and the existing experimental data appeared recently are discussed. The orbital glass is characterized by the coexistence of the orbital paramagnetic state with the superconducting state and occurs at small magnetic fields H c0 c1 . The transition in orbital glass arises at the critical field H c0 which is inversely proportional to the surface cross-area S of an average grain. In connection with theoretical predictions the possible experiments are proposed. (author). 10 refs

The Mars Reconnaissance Orbiter Mission: 10 Years of Exploration from Mars Orbit

Science.gov (United States)

Johnston, M. Daniel; Zurek, Richard W.

2016-01-01

The Mars Reconnaissance Orbiter ( MRO ) entered Mars orbit on March 10, 2006. After five months of aerobraking, a series of propulsive maneuvers were used to establish the desired low -altitude science orbit. The spacecraft has been on station in its 255 x 320 k m, sun -synchronous (approximately 3 am -pm ), primary science orbit since September 2006 performing both scientific and Mars programmatic support functions. This paper will provide a summary of the major achievements of the mission to date and the major flight activities planned for the remainder of its third Extended Mission (EM3). Some of the major flight challenges the flight team has faced are also discussed.

Orbital Infarction due to Sickle Cell Disease without Orbital Pain

Directory of Open Access Journals (Sweden)

Cameron L. McBride

2016-01-01

Full Text Available Sickle cell disease is a hemoglobinopathy that results in paroxysmal arteriolar occlusion and tissue infarction that can manifest in a plurality of tissues. Rarely, these infarcted crises manifest in the bony orbit. Orbital infarction usually presents with acute onset of periorbital tenderness, swelling, erythema, and pain. Soft tissue swelling can result in proptosis and attenuation of extraocular movements. Expedient diagnosis of sickle cell orbital infarction is crucial because this is a potentially sight-threatening entity. Diagnosis can be delayed since the presentation has physical and radiographic findings mimicking various infectious and traumatic processes. We describe a patient who presented with sickle cell orbital crisis without pain. This case highlights the importance of maintaining a high index of suspicion in patients with known sickle cell disease or of African descent born outside the United States in a region where screening for hemoglobinopathy is not routine, even when the presentation is not classic.

Eye and orbital cavity

International Nuclear Information System (INIS)

Panfilova, G.V.; Koval', G.Yu.

1984-01-01

Radioanatomy of eyes and orbit is described. Diseases of the orbit (developmental anomalies, inflammatory diseases, lacrimal apparatus deseases, toxoplasmosis, tumors and cysts et al.), methods of foreign body localization in the eye are considered. Roentgenograms of the orbit and calculation table for foreign body localization in spherical eyes of dissimilar diameter are presented

Local orbit feedback

International Nuclear Information System (INIS)

Anon.

1991-01-01

Critically aligned experiments are sensitive to small changes in the electron beam orbit. At the NSLS storage rings, the electron beam and photon beam motions have been monitored over the past several years. In the survey conducted in 1986 by the NSLS Users Executive Committee, experimenters requested the vertical beam position variation and the vertical angle variation, within a given fill, remain within 10 μm and 10 μr, respectively. This requires improvement in the beam stability by about one order of magnitude. At the NSLS and SSRL storage rings, the beam that is originally centered on the position monitor by a dc orbit correction is observed to have two kinds of motion: a dc drift over a storage period of several hours and a beam bounce about its nominal position. These motions are a result of the equilibrium orbit not being held perfectly stable due to time-varying errors introduced into the magnetic guide field by power supplies, mechanical vibration of the magnets, cooling water temperature variations, etc. The approach to orbit stabilization includes (1) identifying and suppressing as many noise sources on the machine as possible, (2) correcting the beam position globally (see Section 6) by controlling a number of correctors around the circumference of the machine, and (3) correcting the beam position and angle at a given source location by position feedback using local detectors and local orbit bumps. The third approach, called Local Orbit Feedback will be discussed in this section

Quaternary (liquid + liquid) equilibria of aqueous two-phase polyethylene glycol, poly-N-vinylcaprolactam, and KH{sub 2}PO{sub 4}: Experimental and the generalized Flory-Huggins theory

Energy Technology Data Exchange (ETDEWEB)

Foroutan, Masumeh [Department of Physical Chemistry, Faculty of Chemistry, College of Science, University of Tehran, Enghelab Ave., Tehran 14155-6455 (Iran, Islamic Republic of)], E-mail: foroutan@khayam.ut.ac.ir; Zarrabi, Mona [Department of Physical Chemistry, Faculty of Chemistry, College of Science, University of Tehran, Enghelab Ave., Tehran 14155-6455 (Iran, Islamic Republic of)

2008-06-15

A quaternary (liquid + liquid) equilibrium study was performed to focus attention on the interaction parameters between poly-N-vinylcaprolactam (PVCL) and poly-ethylene glycol (PEG) as well as between other species. At first, the new experimental data of (liquid + liquid) equilibria for aqueous two-phase systems containing PEG, KH{sub 2}PO{sub 4}, and PVCL at T = 303.15 K have been determined. Then the Flory-Huggins theory with two electrostatic terms (the Debye-Huckel and the Pitzer-Debye-Huckel equations) has been generalized to correlate the phase behavior of the quaternary system. Good agreement has been found between experimental and calculated data from both models especially from the Pitzer-Debye-Huckel equation. Also an effort was done to compare the effect of temperature as well as addition of PVCL on the binodal curves of PEG, KH{sub 2}PO{sub 4}, and water. The effect of the type of salt on the binodals has been also studied, and the salting out power of the salts has been determined.

Molecular structure and vibrational spectra of Bis(melaminium) terephthalate dihydrate: A DFT computational study

Science.gov (United States)

Tanak, Hasan; Marchewka, Mariusz K.; Drozd, Marek

2013-03-01

The experimental and theoretical vibrational spectra of Bis(melaminium) terephthalate dihydrate were studied. The Fourier transform infrared (FT-IR) spectra of the Bis(melaminium) terephthalate dihydrate and its deuterated analogue were recorded in the solid phase. The molecular geometry and vibrational frequencies of Bis(melaminium) terephthalate dihydrate in the ground state have been calculated by using the density functional method (B3LYP) with 6-31++G(d,p) basis set. The results of the optimized molecular structure are presented and compared with the experimental X-ray diffraction. The molecule contains the weak hydrogen bonds of Nsbnd H⋯O, Nsbnd H⋯N and Osbnd H⋯O types, and those bonds are calculated with DFT method. In addition, molecular electrostatic potential, frontier molecular orbitals and natural bond orbital analysis of the title compound were investigated by theoretical calculations. The lack of the second harmonic generation (SHG) confirms the presence of macroscopic center of inversion.

Validation of Galileo orbits using SLR with a focus on satellites launched into incorrect orbital planes

Science.gov (United States)

Sośnica, Krzysztof; Prange, Lars; Kaźmierski, Kamil; Bury, Grzegorz; Drożdżewski, Mateusz; Zajdel, Radosław; Hadas, Tomasz

2018-02-01

The space segment of the European Global Navigation Satellite System (GNSS) Galileo consists of In-Orbit Validation (IOV) and Full Operational Capability (FOC) spacecraft. The first pair of FOC satellites was launched into an incorrect, highly eccentric orbital plane with a lower than nominal inclination angle. All Galileo satellites are equipped with satellite laser ranging (SLR) retroreflectors which allow, for example, for the assessment of the orbit quality or for the SLR-GNSS co-location in space. The number of SLR observations to Galileo satellites has been continuously increasing thanks to a series of intensive campaigns devoted to SLR tracking of GNSS satellites initiated by the International Laser Ranging Service. This paper assesses systematic effects and quality of Galileo orbits using SLR data with a main focus on Galileo satellites launched into incorrect orbits. We compare the SLR observations with respect to microwave-based Galileo orbits generated by the Center for Orbit Determination in Europe (CODE) in the framework of the International GNSS Service Multi-GNSS Experiment for the period 2014.0-2016.5. We analyze the SLR signature effect, which is characterized by the dependency of SLR residuals with respect to various incidence angles of laser beams for stations equipped with single-photon and multi-photon detectors. Surprisingly, the CODE orbit quality of satellites in the incorrect orbital planes is not worse than that of nominal FOC and IOV orbits. The RMS of SLR residuals is even lower by 5.0 and 1.5 mm for satellites in the incorrect orbital planes than for FOC and IOV satellites, respectively. The mean SLR offsets equal -44.9, -35.0, and -22.4 mm for IOV, FOC, and satellites in the incorrect orbital plane. Finally, we found that the empirical orbit models, which were originally designed for precise orbit determination of GNSS satellites in circular orbits, provide fully appropriate results also for highly eccentric orbits with variable linear

Orbital preservation in a maxillectomy

Energy Technology Data Exchange (ETDEWEB)

Tanaka, Katsuhiko; Nishikawa, Hitomi; Kumagai, Masahiko; Dosaka, Yoshihiro; Kuroda, Toru; Atago, Yoshihiro; Nishio, Masamichi [Sapporo National Hospital (Japan)

1999-07-01

In the past 9 years, 38 patients of the maxillary cancer were treated by a combination of radiation and surgery. Sixteen patients showed the orbital involvement as confirmed by a CT scan and/or MRI. An orbital excenteration was necessary in 6 patients, due mainly to deep intraorbital invasion, while in 10, the orbital contents were preserved despite the involvement of the orbital capsule. The local rate of the orbital region in the latter patients evaluated at 48 months after the initial surgery was 44%. For the treatment of the recurrence at the orbital capsule. The application of gold grain (Au{sup 198}) thus appeared to be a useful tool for further preserving the eye. (author)

Orbital preservation in a maxillectomy

International Nuclear Information System (INIS)

Tanaka, Katsuhiko; Nishikawa, Hitomi; Kumagai, Masahiko; Dosaka, Yoshihiro; Kuroda, Toru; Atago, Yoshihiro; Nishio, Masamichi

1999-01-01

In the past 9 years, 38 patients of the maxillary cancer were treated by a combination of radiation and surgery. Sixteen patients showed the orbital involvement as confirmed by a CT scan and/or MRI. An orbital excenteration was necessary in 6 patients, due mainly to deep intraorbital invasion, while in 10, the orbital contents were preserved despite the involvement of the orbital capsule. The local rate of the orbital region in the latter patients evaluated at 48 months after the initial surgery was 44%. For the treatment of the recurrence at the orbital capsule. The application of gold grain (Au 198 ) thus appeared to be a useful tool for further preserving the eye. (author)

Introducing Earth's Orbital Eccentricity

Science.gov (United States)

Oostra, Benjamin

2015-01-01

Most students know that planetary orbits, including Earth's, are elliptical; that is Kepler's first law, and it is found in many science textbooks. But quite a few are mistaken about the details, thinking that the orbit is very eccentric, or that this effect is somehow responsible for the seasons. In fact, the Earth's orbital eccentricity is…

Application of numerical methods to the determination of molecular wave functions

International Nuclear Information System (INIS)

Douady, Jerome

1969-01-01

A simplified SCF Method is developed. The wave function of molecular systems and spin densities in the case of free radicals are computed from geometrical data. This method, including at the beginning a delocalization of electrons over all the molecular system, two methods which clear out bonding and anti-bonding interactions have been studied and programmed: a) overlap population analysis, b) localisation of molecular orbitals. These methods have been carried out in the case of organic compounds and free radicals. (author) [fr

The Coupled Orbit-Attitude Dynamics and Control of Electric Sail in Displaced Solar Orbits

Directory of Open Access Journals (Sweden)

Mingying Huo

2017-01-01

Full Text Available Displaced solar orbits for spacecraft propelled by electric sails are investigated. Since the propulsive thrust is induced by the sail attitude, the orbital and attitude dynamics of electric-sail-based spacecraft are coupled and required to be investigated together. However, the coupled dynamics and control of electric sails have not been discussed in most published literatures. In this paper, the equilibrium point of the coupled dynamical system in displaced orbit is obtained, and its stability is analyzed through a linearization. The results of stability analysis show that only some of the orbits are marginally stable. For unstable displaced orbits, linear quadratic regulator is employed to control the coupled attitude-orbit system. Numerical simulations show that the proposed strategy can control the coupled system and a small torque can stabilize both the attitude and orbit. In order to generate the control force and torque, the voltage distribution problem is studied in an optimal framework. The numerical results show that the control force and torque of electric sail can be realized by adjusting the voltage distribution of charged tethers.

Application of orbital strong magnet in the extraction of deep orbital magnetic foreign bodies

Directory of Open Access Journals (Sweden)

Jin-Chen Jia

2017-12-01

Full Text Available AIM: To investigate the surgical method and efficacy of extraction of deep orbital magnetic foreign bodies by mean of an orbital strong magnet. METHODS: A retrospective analysis of clinical data of patients with deep orbital magnetic foreign bodies(OMFBin Hebei Eye Hospital from June 2014 to May 2017 was processed. A total of 23 eyes were enrolled, among them, 14 eyes of extraorbital OMFB, 9 eyes of intraorbital OMFB. The rate of extraction of foreign bodies and the postoperative complications were observed. RESULTS: All eyes of intraorbital foreign bodies were successfully extracted with 100% success rate. Twelve of 14 eyes of extraorbital foreign bodies were extracted with 86% success rate. Mild orbital hemorrhage were found in 2 eyes. There was no other obvious complication such as visual loss, orbital massive hemorrhage or limited ocular movement. CONCLUSION: It's an ideal surgical method to extract the deep orbital magnetic foreign bodies by mean of an orbital strong magnet, with mini-injury, high success rate, short duration and few complications.

Intra-molecular Charge Transfer and Electron Delocalization in Non-fullerene Organic Solar Cells

Energy Technology Data Exchange (ETDEWEB)

Wu, Qinghe [Department of Chemistry, Key Laboratory for Preparation and Application of Ordered Structural Materials of Guangdong Province, Shantou University, Guangdong 515063, P. R. China; Zhao, Donglin [Department of Chemistry, The James Franck Institute, The University of Chicago, 929 E 57th Street, Chicago, Illinois 60637, United States; Goldey, Matthew B. [Institute for Molecular Engineering, The University of Chicago, 5747 South Ellis Avenue, Chicago, Illinois 60637, United States; Filatov, Alexander S. [Department of Chemistry, The James Franck Institute, The University of Chicago, 929 E 57th Street, Chicago, Illinois 60637, United States; Sharapov, Valerii [Department of Chemistry, The James Franck Institute, The University of Chicago, 929 E 57th Street, Chicago, Illinois 60637, United States; Colón, Yamil J. [Institute for Molecular Engineering, Materials Science Division, Argonne National Laboratory, 9700 Cass Avenue, Lemont, Illinois 60439, United States; Institute for Molecular Engineering, The University of Chicago, 5747 South Ellis Avenue, Chicago, Illinois 60637, United States; Cai, Zhengxu [Department of Chemistry, The James Franck Institute, The University of Chicago, 929 E 57th Street, Chicago, Illinois 60637, United States; Chen, Wei [Institute for Molecular Engineering, Materials Science Division, Argonne National Laboratory, 9700 Cass Avenue, Lemont, Illinois 60439, United States; Institute for Molecular Engineering, The University of Chicago, 5747 South Ellis Avenue, Chicago, Illinois 60637, United States; de Pablo, Juan [Institute for Molecular Engineering, Materials Science Division, Argonne National Laboratory, 9700 Cass Avenue, Lemont, Illinois 60439, United States; Institute for Molecular Engineering, The University of Chicago, 5747 South Ellis Avenue, Chicago, Illinois 60637, United States; Galli, Giulia [Institute for Molecular Engineering, Materials Science Division, Argonne National Laboratory, 9700 Cass Avenue, Lemont, Illinois 60439, United States; Institute for Molecular Engineering, The University of Chicago, 5747 South Ellis Avenue, Chicago, Illinois 60637, United States; Yu, Luping [Department of Chemistry, The James Franck Institute, The University of Chicago, 929 E 57th Street, Chicago, Illinois 60637, United States

2018-03-02

Two types of electron acceptors were synthesized by coupling two kinds of electron-rich cores with four equivalent perylene diimides (PDIs) at the a position. With fully aromatic cores, TPB and TPSe have pi-orbitals spread continuously over the whole aromatic conjugated backbone, unlike TPC and TPSi, which contain isolated PDI units due to the use of a tetrahedron carbon or silicon linker. Density functional theory calculations of the projected density of states showed that the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) for TPB are localized in separate regions of space. Further, the LUMO of TPB shows a greater contribution from the orbitals belonging to the connective core of the molecules than that of TPC. Overall, the properties of the HOMO and LUMO point at increased intra-molecular delocalization of negative charge carriers for TPB and TPSe than for TPC and TPSi and hence at a more facile intra-molecular charge transfer for the former. The film absorption and emission spectra showed evidences for the inter -molecular electron delocalization in TPB and TPSe, which is consistent with the network structure revealed by X-ray diffraction studies on single crystals of TPB. These features benefit the formation of charge transfer states and/or facilitate charge transport. Thus, higher electron mobility and higher charge dissociation probabilities under J(sc) condition were observed in blend films of TPB:PTB7-Th and TPSe:PTB7-Th than those in TPC:PTB7Th and TPSi:PTB7-Th blend films. As a result, the J(sc) and fill factor values of 15.02 mA/cm(2), 0.58 and 14.36 mA/cm(2), 0.55 for TPB- and TPSe-based solar cell are observed, whereas those for TPC and TPSi are 11.55 mA/cm2, 0.47 and 10.35 mA/cm(2), 0.42, respectively.

Congenital orbital teratoma.

Science.gov (United States)

Aiyub, Shereen; Chan, Wengonn; Szetu, John; Sullivan, Laurence J; Pater, John; Cooper, Peter; Selva, Dinesh

2013-12-01

We present a case of mature congenital orbital teratoma managed with lid-sparing exenteration and dermis fat graft. This is a case report on the management of congenital orbital teratoma. A full-term baby was born in Fiji with prolapsed right globe which was surrounded by a nonpulsatile, cystic mass. Clinical and imaging features were consistent with congenital orbital teratoma. Due to limited surgical expertise, the patient was transferred to Adelaide, Australia for further management. The patient underwent a lid-sparing exenteration with frozen section control of the apical margin. A dermis fat graft from the groin was placed beneath the lid skin to provide volume. Histopathology revealed mature tissues from each of the three germ cell layers which confirmed the diagnosis of mature teratoma. We describe the successful use of demis fat graft in socket reconstruction following lid-sparing exenteration for congenital orbital teratoma.

Congenital orbital teratoma

Directory of Open Access Journals (Sweden)

Shereen Aiyub

2013-01-01

Full Text Available We present a case of mature congenital orbital teratoma managed with lid-sparing exenteration and dermis fat graft. This is a case report on the management of congenital orbital teratoma. A full-term baby was born in Fiji with prolapsed right globe which was surrounded by a nonpulsatile, cystic mass. Clinical and imaging features were consistent with congenital orbital teratoma. Due to limited surgical expertise, the patient was transferred to Adelaide, Australia for further management. The patient underwent a lid-sparing exenteration with frozen section control of the apical margin. A dermis fat graft from the groin was placed beneath the lid skin to provide volume. Histopathology revealed mature tissues from each of the three germ cell layers which confirmed the diagnosis of mature teratoma. We describe the successful use of demis fat graft in socket reconstruction following lid-sparing exenteration for congenital orbital teratoma.

Orbit Determination of Spacecraft in Earth-Moon L1 and L2 Libration Point Orbits

Science.gov (United States)

Woodard, Mark; Cosgrove, Daniel; Morinelli, Patrick; Marchese, Jeff; Owens, Brandon; Folta, David

2011-01-01

The ARTEMIS mission, part of the THEMIS extended mission, is the first to fly spacecraft in the Earth-Moon Lissajous regions. In 2009, two of the five THEMIS spacecraft were redeployed from Earth-centered orbits to arrive in Earth-Moon Lissajous orbits in late 2010. Starting in August 2010, the ARTEMIS P1 spacecraft executed numerous stationkeeping maneuvers, initially maintaining a lunar L2 Lissajous orbit before transitioning into a lunar L1 orbit. The ARTEMIS P2 spacecraft entered a L1 Lissajous orbit in October 2010. In April 2011, both ARTEMIS spacecraft will suspend Lissajous stationkeeping and will be maneuvered into lunar orbits. The success of the ARTEMIS mission has allowed the science team to gather unprecedented magnetospheric measurements in the lunar Lissajous regions. In order to effectively perform lunar Lissajous stationkeeping maneuvers, the ARTEMIS operations team has provided orbit determination solutions with typical accuracies on the order of 0.1 km in position and 0.1 cm/s in velocity. The ARTEMIS team utilizes the Goddard Trajectory Determination System (GTDS), using a batch least squares method, to process range and Doppler tracking measurements from the NASA Deep Space Network (DSN), Berkeley Ground Station (BGS), Merritt Island (MILA) station, and United Space Network (USN). The team has also investigated processing of the same tracking data measurements using the Orbit Determination Tool Kit (ODTK) software, which uses an extended Kalman filter and recursive smoother to estimate the orbit. The orbit determination results from each of these methods will be presented and we will discuss the advantages and disadvantages associated with using each method in the lunar Lissajous regions. Orbit determination accuracy is dependent on both the quality and quantity of tracking measurements, fidelity of the orbit force models, and the estimation techniques used. Prior to Lissajous operations, the team determined the appropriate quantity of tracking

STABLE CONIC-HELICAL ORBITS OF PLANETS AROUND BINARY STARS: ANALYTICAL RESULTS

Energy Technology Data Exchange (ETDEWEB)

Oks, E. [Physics Department, 206 Allison Lab., Auburn University, Auburn, AL 36849 (United States)

2015-05-10

Studies of planets in binary star systems are especially important because it was estimated that about half of binary stars are capable of supporting habitable terrestrial planets within stable orbital ranges. One-planet binary star systems (OBSS) have a limited analogy to objects studied in atomic/molecular physics: one-electron Rydberg quasimolecules (ORQ). Specifically, ORQ, consisting of two fully stripped ions of the nuclear charges Z and Z′ plus one highly excited electron, are encountered in various plasmas containing more than one kind of ion. Classical analytical studies of ORQ resulted in the discovery of classical stable electronic orbits with the shape of a helix on the surface of a cone. In the present paper we show that despite several important distinctions between OBSS and ORQ, it is possible for OBSS to have stable planetary orbits in the shape of a helix on a conical surface, whose axis of symmetry coincides with the interstellar axis; the stability is not affected by the rotation of the stars. Further, we demonstrate that the eccentricity of the stars’ orbits does not affect the stability of the helical planetary motion if the center of symmetry of the helix is relatively close to the star of the larger mass. We also show that if the center of symmetry of the conic-helical planetary orbit is relatively close to the star of the smaller mass, a sufficiently large eccentricity of stars’ orbits can switch the planetary motion to the unstable mode and the planet would escape the system. We demonstrate that such planets are transitable for the overwhelming majority of inclinations of plane of the stars’ orbits (i.e., the projections of the planet and the adjacent start on the plane of the sky coincide once in a while). This means that conic-helical planetary orbits at binary stars can be detected photometrically. We consider, as an example, Kepler-16 binary stars to provide illustrative numerical data on the possible parameters and the

Polarized atomic orbitals for linear scaling methods

Science.gov (United States)

Berghold, Gerd; Parrinello, Michele; Hutter, Jürg

2002-02-01

We present a modified version of the polarized atomic orbital (PAO) method [M. S. Lee and M. Head-Gordon, J. Chem. Phys. 107, 9085 (1997)] to construct minimal basis sets optimized in the molecular environment. The minimal basis set derives its flexibility from the fact that it is formed as a linear combination of a larger set of atomic orbitals. This approach significantly reduces the number of independent variables to be determined during a calculation, while retaining most of the essential chemistry resulting from the admixture of higher angular momentum functions. Furthermore, we combine the PAO method with linear scaling algorithms. We use the Chebyshev polynomial expansion method, the conjugate gradient density matrix search, and the canonical purification of the density matrix. The combined scheme overcomes one of the major drawbacks of standard approaches for large nonorthogonal basis sets, namely numerical instabilities resulting from ill-conditioned overlap matrices. We find that the condition number of the PAO overlap matrix is independent from the condition number of the underlying extended basis set, and consequently no numerical instabilities are encountered. Various applications are shown to confirm this conclusion and to compare the performance of the PAO method with extended basis-set calculations.

Perturbation expansion theory corrected from basis set superposition error. I. Locally projected excited orbitals and single excitations.

Science.gov (United States)

Nagata, Takeshi; Iwata, Suehiro

2004-02-22

The locally projected self-consistent field molecular orbital method for molecular interaction (LP SCF MI) is reformulated for multifragment systems. For the perturbation expansion, two types of the local excited orbitals are defined; one is fully local in the basis set on a fragment, and the other has to be partially delocalized to the basis sets on the other fragments. The perturbation expansion calculations only within single excitations (LP SE MP2) are tested for water dimer, hydrogen fluoride dimer, and colinear symmetric ArM+ Ar (M = Na and K). The calculated binding energies of LP SE MP2 are all close to the corresponding counterpoise corrected SCF binding energy. By adding the single excitations, the deficiency in LP SCF MI is thus removed. The results suggest that the exclusion of the charge-transfer effects in LP SCF MI might indeed be the cause of the underestimation for the binding energy. (c) 2004 American Institute of Physics.

Photoelectron and UV absorption spectroscopy for determination of electronic configurations of negative molecular ions: Chlorophenols

International Nuclear Information System (INIS)

Tseplin, E.E.; Tseplina, S.N.; Tuimedov, G.M.; Khvostenko, O.G.

2009-01-01

The photoelectron and UV absorption spectra of p-, m-, and o-chlorophenols in the gas phase have been obtained. On the basis of DFT B3LYP/6-311++G(d, p) calculations, the photoelectron bands have been assigned to occupied molecular orbitals. From the TDDFT B3LYP/6-311++G(d, p) calculation results, the UV absorption bands have been assigned to excited singlet states of the molecules under investigation. For each excited state a dominant transition was found. It has been shown that the energies of these singlet transitions correlate with the energy differences between the ground-state molecular orbitals participating in them. Using the UV spectra interpretation, the electronic states of molecular anions detected earlier for the same compounds by means of the resonant electron capture mass-spectrometry have been determined.

Nuclear molecular states

International Nuclear Information System (INIS)

Abe, Y.

1975-01-01

The effects of polarization on the stability of α-cluster structures in 8 Be and 12 C nuclei are studied in the intrinsic states. The extent of the polarization of α-clusters is investigated by employing a molecular-orbital model. Two α-cluster structure of 8 Be is shown to be extremely stable, and a triangular configuration of three α-clusters is also shown to be stable, but the polarizations of α-clusters are found rather large. Gruemmer--Faessler's method is discussed and their results are shown to be trivial

Radiology of orbital trauma

International Nuclear Information System (INIS)

Kelly, J.K.; Lazo, A.; Metes, J.J.

1988-01-01

Computed tomography has become the gold standard against which to measure orbital imaging modalities. The simultaneous display of bone, soft tissues, paranasal sinuses, and intracranial structures is a unique advantage. Radiation dose and cost have been cited as disadvantages. These would suggest that CT be reserved for the patient with significant orbital injury or difficult diagnostic problems. Magnetic resonance is limited in the investigation of orbital trauma

A new approach to the method of source-sink potentials for molecular conduction

Energy Technology Data Exchange (ETDEWEB)

Pickup, Barry T., E-mail: B.T.Pickup@sheffield.ac.uk, E-mail: P.W.Fowler@sheffield.ac.uk; Fowler, Patrick W., E-mail: B.T.Pickup@sheffield.ac.uk, E-mail: P.W.Fowler@sheffield.ac.uk; Borg, Martha [Department of Chemistry, University of Sheffield, Sheffield S3 7HF (United Kingdom); Sciriha, Irene [Department of Mathematics, University of Malta, Msida (Malta)

2015-11-21

We re-derive the tight-binding source-sink potential (SSP) equations for ballistic conduction through conjugated molecular structures in a form that avoids singularities. This enables derivation of new results for families of molecular devices in terms of eigenvectors and eigenvalues of the adjacency matrix of the molecular graph. In particular, we define the transmission of electrons through individual molecular orbitals (MO) and through MO shells. We make explicit the behaviour of the total current and individual MO and shell currents at molecular eigenvalues. A rich variety of behaviour is found. A SSP device has specific insulation or conduction at an eigenvalue of the molecular graph (a root of the characteristic polynomial) according to the multiplicities of that value in the spectra of four defined device polynomials. Conduction near eigenvalues is dominated by the transmission curves of nearby shells. A shell may be inert or active. An inert shell does not conduct at any energy, not even at its own eigenvalue. Conduction may occur at the eigenvalue of an inert shell, but is then carried entirely by other shells. If a shell is active, it carries all conduction at its own eigenvalue. For bipartite molecular graphs (alternant molecules), orbital conduction properties are governed by a pairing theorem. Inertness of shells for families such as chains and rings is predicted by selection rules based on node counting and degeneracy.

Manipulation and application of orbital ordering

International Nuclear Information System (INIS)

Sheng Zhigao; Sun Yuping

2014-01-01

Under certain conditions, the orbits of the outmost shell electrons in strong correlated materials can be localized in order, which gives birth to so-called orbital ordering. During the construction or destruction of the orbital ordering, strongly correlated materials show fruitful quantum critical phenomena with great potential for future applications. We first present the mechanism for the construction of orbital ordering. Then, some physical properties associated with orbits are discussed. Finally, we emphasize the key points and progress in the research of orbital ordering controlling. (authors)

Pictorial essay: Orbital tuberculosis

International Nuclear Information System (INIS)

Narula, Mahender K; Chaudhary, Vikas; Baruah, Dhiraj; Kathuria, Manoj; Anand, Rama

2010-01-01

Tuberculosis of the orbit is rare, even in places where tuberculosis is endemic. The disease may involve soft tissue, the lacrimal gland, or the periosteum or bones of the orbital wall. Intracranial extension, in the form of extradural abscess, and infratemporal fossa extension has been described. This pictorial essay illustrates the imaging findings of nine histopathologically confirmed cases of orbital tuberculosis. All these patients responded to antituberculous treatment

Traumatic orbital encephalocele: Presentation and imaging.

Science.gov (United States)

Wei, Leslie A; Kennedy, Tabassum A; Paul, Sean; Wells, Timothy S; Griepentrog, Greg J; Lucarelli, Mark J

2016-01-01

Traumatic orbital encephalocele is a rare but severe complication of orbital roof fractures. We describe 3 cases of orbital encephalocele due to trauma in children. Retrospective case series from the University of Wisconsin - Madison and Medical College of Wisconsin. Three cases of traumatic orbital encephalocele in pediatric patients were found. The mechanism of injury was motor vehicle accident in 2 patients and accidental self-inflicted gunshot wound in 1 patient. All 3 patients sustained orbital roof fractures (4 mm to 19 mm in width) and frontal lobe contusions with high intracranial pressure. A key finding in all 3 cases was progression of proptosis and globe displacement 4 to 11 days after initial injury. On initial CT, all were diagnosed with extraconal hemorrhage adjacent to the roof fractures, with subsequent enlargement of the mass and eventual diagnosis of encephalocele. Orbital encephalocele is a severe and sight-threatening complication of orbital roof fractures. Post-traumatic orbital encephalocele can be challenging to diagnose on CT as patients with this condition often have associated orbital and intracranial hematoma, which can be difficult to distinguish from herniated brain tissue. When there is a high index of suspicion for encephalocele, an MRI of the orbits and brain with contrast should be obtained for additional characterization. Imaging signs that should raise suspicion for traumatic orbital encephalocele include an enlarging heterogeneous orbital mass in conjunction with a roof fracture and/or widening fracture segments.

PS Booster Orbit Correction

CERN Document Server

Chanel, M; Rumolo, G; Tomás, R; CERN. Geneva. AB Department

2008-01-01

At the end of the 2007 run, orbit measurements were carried out in the 4 rings of the PS Booster (PSB) for different working points and beam energies. The aim of these measurements was to provide the necessary input data for a PSB realignment campaign during the 2007/2008 shutdown. Currently, only very few corrector magnets can be operated reliably in the PSB; therefore the orbit correction has to be achieved by displacing (horizontally and vertically) and/or tilting some of the defocusing quadrupoles (QDs). In this report we first describe the orbit measurements, followed by a detailed explanation of the orbit correction strategy. Results and conclusions are presented in the last section.

Effects of DeOrbitSail as applied to Lifetime predictions of Low Earth Orbit Satellites

Science.gov (United States)

Afful, Andoh; Opperman, Ben; Steyn, Herman

2016-07-01

Orbit lifetime prediction is an important component of satellite mission design and post-launch space operations. Throughout its lifetime in space, a spacecraft is exposed to risk of collision with orbital debris or operational satellites. This risk is especially high within the Low Earth Orbit (LEO) region where the highest density of space debris is accumulated. This paper investigates orbital decay of some LEO micro-satellites and accelerating orbit decay by using a deorbitsail. The Semi-Analytical Liu Theory (SALT) and the Satellite Toolkit was employed to determine the mean elements and expressions for the time rates of change. Test cases of observed decayed satellites (Iridium-85 and Starshine-1) are used to evaluate the predicted theory. Results for the test cases indicated that the theory fitted observational data well within acceptable limits. Orbit decay progress of the SUNSAT micro-satellite was analysed using relevant orbital parameters derived from historic Two Line Element (TLE) sets and comparing with decay and lifetime prediction models. This paper also explored the deorbit date and time for a 1U CubeSat (ZACUBE-01). The use of solar sails as devices to speed up the deorbiting of LEO satellites is considered. In a drag sail mode, the deorbitsail technique significantly increases the effective cross-sectional area of a satellite, subsequently increasing atmospheric drag and accelerating orbit decay. The concept proposed in this study introduced a very useful technique of orbit decay as well as deorbiting of spacecraft.

Use of Orbital Conformer to Improve Speech in Patients with Confluent Maxillectomy and Orbital Defects

Science.gov (United States)

Colebeck, Amanda C.; Kase, Michael T.; Nichols, Cindy B.; Golden, Marjorie; Huryn, Joseph M.

2016-01-01

The basic objective in prosthetic restoration of confluent maxillary and orbital defects is to achieve a comfortable, cosmetically acceptable prosthesis that restores speech, deglutition, and mastication. It is a challenging task complicated by the size and shape of the defects. The maxillary obturator prosthesis often satisfies the objective of adequate deglutition; however, orbital defects that are not obturated in the medial septal or posterior walls allow air to escape, negatively impacting phonation. This article describes a technique to achieve favorable prosthetic rehabilitation in a patient with a maxillectomy and ipsilateral orbital exenteration. The prosthetic components include maxillary obturator, orbital conformer, and orbital prosthesis connected using rigid magnetic attachments. PMID:25953143

Robustness analysis method for orbit control

Science.gov (United States)

Zhang, Jingrui; Yang, Keying; Qi, Rui; Zhao, Shuge; Li, Yanyan

2017-08-01

Satellite orbits require periodical maintenance due to the presence of perturbations. However, random errors caused by inaccurate orbit determination and thrust implementation may lead to failure of the orbit control strategy. Therefore, it is necessary to analyze the robustness of the orbit control methods. Feasible strategies which are tolerant to errors of a certain magnitude can be developed to perform reliable orbit control for the satellite. In this paper, first, the orbital dynamic model is formulated by Gauss' form of the planetary equation using the mean orbit elements; the atmospheric drag and the Earth's non-spherical perturbations are taken into consideration in this model. Second, an impulsive control strategy employing the differential correction algorithm is developed to maintain the satellite trajectory parameters in given ranges. Finally, the robustness of the impulsive control method is analyzed through Monte Carlo simulations while taking orbit determination error and thrust error into account.

Chemical bonding analysis for solid-state systems using intrinsic oriented quasiatomic minimal-basis-set orbitals

International Nuclear Information System (INIS)

Yao, Y.X.; Wang, C.Z.; Ho, K.M.

2010-01-01

A chemical bonding scheme is presented for the analysis of solid-state systems. The scheme is based on the intrinsic oriented quasiatomic minimal-basis-set orbitals (IO-QUAMBOs) previously developed by Ivanic and Ruedenberg for molecular systems. In the solid-state scheme, IO-QUAMBOs are generated by a unitary transformation of the quasiatomic orbitals located at each site of the system with the criteria of maximizing the sum of the fourth power of interatomic orbital bond order. Possible bonding and antibonding characters are indicated by the single particle matrix elements, and can be further examined by the projected density of states. We demonstrate the method by applications to graphene and (6,0) zigzag carbon nanotube. The oriented-orbital scheme automatically describes the system in terms of sp 2 hybridization. The effect of curvature on the electronic structure of the zigzag carbon nanotube is also manifested in the deformation of the intrinsic oriented orbitals as well as a breaking of symmetry leading to nonzero single particle density matrix elements. In an additional study, the analysis is performed on the Al 3 V compound. The main covalent bonding characters are identified in a straightforward way without resorting to the symmetry analysis. Our method provides a general way for chemical bonding analysis of ab initio electronic structure calculations with any type of basis sets.

Orbiter OMS and RCS technology

Science.gov (United States)

Boudreaux, R. A.

1982-01-01

Orbiter Orbital Maneuver Subsystem (OMS) and Reaction Control Subsystem (RCS) tankage has proved to be highly successful in shuttle flights on-orbit propellant transfer tests were done. Tank qualification tests along with flight demonstrations were carried out future uses of storable propellants are cited.

Unusual solvation through both p-orbital lobes of a carbene carbon

Energy Technology Data Exchange (ETDEWEB)

Hadad, C. Z., E-mail: cacier.hadad@udea.edu.co [Grupo de Química-Física Teórica, Instituto de Química, Universidad de Antioquia, A. A. 1226 Medellín (Colombia); Jenkins, Samantha [College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, Hunan 410081 (China); Flórez, Elizabeth [Departamento de Ciencias Básicas, Universidad de Medellín, Carrera 87 N° 30-65, Medellín (Colombia)

2015-03-07

As a result of a configurational space search done to explain the experimental evidence of transient specific solvation of singlet fluorocarbene amide with tetrahydrofuran, we found that the most stable structures consist in a group in which each oxygen of two tetrahydrofuran molecules act as electron donor to its respective empty p-orbital lobe of the carbene carbon atom, located at each side of the carbene molecular plane. This kind of species, which to our knowledge has not been reported before, explains very well the particular experimental characteristics observed for the transient solvation of this system. We postulate that the simultaneous interaction to both p-orbital lobes seems to confer a special stability to the solvation complexes, because this situation moves away the systems from the proximity of the corresponding transition states for the ylide products. Additionally, we present an analysis of other solvation complexes and a study of the nature of the involved interactions.

Calculations of the excitation energies of all-trans and 11,12s-dicis retinals using localized molecular orbitals obtained by the elongation method

Science.gov (United States)

Kurihara, Youji; Aoki, Yuriko; Imamura, Akira

1997-09-01

In the present article, the excitation energies of the all-trans and the 11,12s-dicis retinals were calculated by using the elongation method. The geometries of these molecules were optimized with the 4-31G basis set by using the GAUSSIAN 92 program. The wave functions for the calculation of the excitation energies were obtained with CNDO/S approximation by the elongation method, which enables us to analyze electronic structures of aperiodic polymers in terms of the exciton-type local excitation and the charge transfer-type excitation. The excitation energies were calculated by using the single excitation configuration interaction (SECI) on the basis of localized molecular orbitals (LMOs). The LMOs were obtained in the process of the elongation method. The configuration interaction (CI) matrices were diagonalized by Davidson's method. The calculated results were in good agreement with the experimental data for absorption spectra. In order to consider the isomerization path from 11,12s-dicis to all-trans retinals, the barriers to the rotations about C11-C12 double and C12-C13 single bonds were evaluated.

Theory of Covalent Adsorbate Frontier Orbital Energies on Functionalized Light-Absorbing Semiconductor Surfaces.

Science.gov (United States)

Yu, Min; Doak, Peter; Tamblyn, Isaac; Neaton, Jeffrey B

2013-05-16

Functional hybrid interfaces between organic molecules and semiconductors are central to many emerging information and solar energy conversion technologies. Here we demonstrate a general, empirical parameter-free approach for computing and understanding frontier orbital energies - or redox levels - of a broad class of covalently bonded organic-semiconductor surfaces. We develop this framework in the context of specific density functional theory (DFT) and many-body perturbation theory calculations, within the GW approximation, of an exemplar interface, thiophene-functionalized silicon (111). Through detailed calculations taking into account structural and binding energetics of mixed-monolayers consisting of both covalently attached thiophene and hydrogen, chlorine, methyl, and other passivating groups, we quantify the impact of coverage, nonlocal polarization, and interface dipole effects on the alignment of the thiophene frontier orbital energies with the silicon band edges. For thiophene adsorbate frontier orbital energies, we observe significant corrections to standard DFT (∼1 eV), including large nonlocal electrostatic polarization effects (∼1.6 eV). Importantly, both results can be rationalized from knowledge of the electronic structure of the isolated thiophene molecule and silicon substrate systems. Silicon band edge energies are predicted to vary by more than 2.5 eV, while molecular orbital energies stay similar, with the different functional groups studied, suggesting the prospect of tuning energy alignment over a wide range for photoelectrochemistry and other applications.

[Secondary orbital lymphoma].

Science.gov (United States)

Basanta, I; Sevillano, C; Álvarez, M D

2015-09-01

A case is presented of an 85 year-old Caucasian female with lymphoma that recurred in the orbit (secondary ocular adnexal lymphoma). The orbital tumour was a diffuse large B-cell lymphoma according to the REAL classification (Revised European-American Lymphoma Classification). Orbital lymphomas are predominantly B-cell proliferations of a variety of histological types, and most are low-grade tumours. Patients are usually middle-aged or elderly, and it is slightly more common in women. A palpable mass, proptosis and blepharoptosis are the most common signs of presentation. Copyright © 2011 Sociedad Española de Oftalmología. Published by Elsevier España, S.L.U. All rights reserved.

Extended Hu¨ckel Calculations on Solids Using the Avogadro Molecular Editor and Visualizer

Science.gov (United States)

Avery, Patrick; Ludoweig, Herbert; Autschbach, Jochen; Zurek, Eva

2018-01-01

The "Yet Another extended Hu¨ckel Molecular Orbital Package" (YAeHMOP) has been merged with the Avogadro open-source molecular editor and visualizer. It is now possible to perform YAeHMOP calculations directly from the Avogadro graphical user interface for materials that are periodic in one, two, or three dimensions, and to visualize…

JSC Orbital Debris Website Description

Science.gov (United States)

Johnson, Nicholas L.

2006-01-01

Purpose: The website provides information about the NASA Orbital Debris Program Office at JSC, which is the lead NASA center for orbital debris research. It is recognized world-wide for its leadership in addressing orbital debris issues. The NASA Orbital Debris Program Office has taken the international lead in conducting measurements of the environment and in developing the technical consensus for adopting mitigation measures to protect users of the orbital environment. Work at the center continues with developing an improved understanding of the orbital debris environment and measures that can be taken to control its growth. Major Contents: Orbital Debris research is divided into the following five broad efforts. Each area of research contains specific information as follows: 1) Modeling - NASA scientists continue to develop and upgrade orbital debris models to describe and characterize the current and future debris environment. Evolutionary and engineering models are described in detail. Downloadable items include a document in PDF format and executable software. 2) Measurements - Measurements of near-Earth orbital debris are accomplished by conducting ground-based and space-based observations of the orbital debris environment. The data from these sources provide validation of the environment models and identify the presence of new sources. Radar, optical and surface examinations are described. External links to related topics are provided. 3) Protection - Orbital debris protection involves conducting hypervelocity impact measurements to assess the risk presented by orbital debris to operating spacecraft and developing new materials and new designs to provide better protection from the environment with less weight penalty. The data from this work provides the link between the environment defined by the models and the risk presented by that environment to operating spacecraft and provides recommendations on design and operations procedures to reduce the risk as

Shuttlecock-Shaped Molecular Rectifier: Asymmetric Electron Transport Coupled with Controlled Molecular Motion.

Science.gov (United States)

Ryu, Taekhee; Lansac, Yves; Jang, Yun Hee

2017-07-12

A fullerene derivative with five hydroxyphenyl groups attached around a pentagon, (4-HOC 6 H 4 ) 5 HC 60 (1), has shown an asymmetric current-voltage (I-V) curve in a conducting atomic force microscopy experiment on gold. Such molecular rectification has been ascribed to the asymmetric distribution of frontier molecular orbitals over its shuttlecock-shaped structure. Our nonequilibrium Green's function (NEGF) calculations based on density functional theory (DFT) indeed exhibit an asymmetric I-V curve for 1 standing up between two Au(111) electrodes, but the resulting rectification ratio (RR ∼ 3) is insufficient to explain the wide range of RR observed in experiments performed under a high bias voltage. Therefore, we formulate a hypothesis that high RR (>10) may come from molecular orientation switching induced by a strong electric field applied between two electrodes. Indeed, molecular dynamics simulations of a self-assembled monolayer of 1 on Au(111) show that the orientation of 1 can be switched between standing-up and lying-on-the-side configurations in a manner to align its molecular dipole moment with the direction of the applied electric field. The DFT-NEGF calculations taking into account such field-induced reorientation between up and side configurations indeed yield RR of ∼13, which agrees well with the experimental value obtained under a high bias voltage.

Negative differential resistance and switch behavior of T-BxNy (x, y = 5, 6, 11) molecular junctions

Science.gov (United States)

Wang, Shi-Liang; Yang, Chuan-Lu; Wang, Mei-Shan; Ma, Xiao-Guang; Xin, Jian-Guo

2017-05-01

The electronic transport properties of T-BxNy (x, y = 5, 6, 11) molecular junction are investigated based on first-principle density functional theory and non-equilibrium Green's function method. Strong negative differential resistance (NDR) behavior is observed for T-B5N6 molecule under negative and positive bias voltages, with an obvious switch effect for T-B6N5. However, only small NDR is shown for the complex of the two molecules. The projected device density of states, the spatial distribution of molecular orbitals, and the effect of transmission spectra under various bias voltages on the electronic transport properties are analyzed. The obvious effect of bias voltage on the changes in the electronic distribution of frontier molecular orbitals is responsible for the NDR or switch behavior. Therefore, different functional molecular devices can be obtained with different structures of T-BxNy.

Orbits in weak and strong bars

CERN Document Server

Contopoulos, George

1980-01-01

The authors study the plane orbits in simple bar models embedded in an axisymmetric background when the bar density is about 1% (weak), 10% (intermediate) or 100% (strong bar) of the axisymmetric density. Most orbits follow the stable periodic orbits. The basic families of periodic orbits are described. In weak bars with two Inner Lindblad Resonances there is a family of stable orbits extending from the center up to the Outer Lindblad Resonance. This family contains the long period orbits near corotation. Other stable families appear between the Inner Lindblad Resonances, outside the Outer Lindblad Resonance, around corotation (short period orbits) and around the center (retrograde). Some families become unstable or disappear in strong bars. A comparison is made with cases having one or no Inner Lindblad Resonance. (12 refs).

The Eccentric Behavior of Nearly Frozen Orbits

Science.gov (United States)

Sweetser, Theodore H.; Vincent, Mark A.

2013-01-01

Frozen orbits are orbits which have only short-period changes in their mean eccentricity and argument of periapse, so that they basically keep a fixed orientation within their plane of motion. Nearly frozen orbits are those whose eccentricity and argument of periapse have values close to those of a frozen orbit. We call them "nearly" frozen because their eccentricity vector (a vector whose polar coordinates are eccentricity and argument of periapse) will stay within a bounded distance from the frozen orbit eccentricity vector, circulating around it over time. For highly inclined orbits around the Earth, this distance is effectively constant over time. Furthermore, frozen orbit eccentricity values are low enough that these orbits are essentially eccentric (i.e., off center) circles, so that nearly frozen orbits around Earth are bounded above and below by frozen orbits.

GLONASS orbit/clock combination in VNIIFTRI

Science.gov (United States)

Bezmenov, I.; Pasynok, S.

2015-08-01

An algorithm and a program for GLONASS satellites orbit/clock combination based on daily precise orbits submitted by several Analytic Centers were developed. Some theoretical estimates for combine orbit positions RMS were derived. It was shown that under condition that RMS of satellite orbits provided by the Analytic Centers during a long time interval are commensurable the RMS of combine orbit positions is no greater than RMS of other satellite positions estimated by any of the Analytic Centers.

Nuclear-electronic orbital reduced explicitly correlated Hartree-Fock approach: Restricted basis sets and open-shell systems

International Nuclear Information System (INIS)

Brorsen, Kurt R.; Sirjoosingh, Andrew; Pak, Michael V.; Hammes-Schiffer, Sharon

2015-01-01

The nuclear electronic orbital (NEO) reduced explicitly correlated Hartree-Fock (RXCHF) approach couples select electronic orbitals to the nuclear orbital via Gaussian-type geminal functions. This approach is extended to enable the use of a restricted basis set for the explicitly correlated electronic orbitals and an open-shell treatment for the other electronic orbitals. The working equations are derived and the implementation is discussed for both extensions. The RXCHF method with a restricted basis set is applied to HCN and FHF − and is shown to agree quantitatively with results from RXCHF calculations with a full basis set. The number of many-particle integrals that must be calculated for these two molecules is reduced by over an order of magnitude with essentially no loss in accuracy, and the reduction factor will increase substantially for larger systems. Typically, the computational cost of RXCHF calculations with restricted basis sets will scale in terms of the number of basis functions centered on the quantum nucleus and the covalently bonded neighbor(s). In addition, the RXCHF method with an odd number of electrons that are not explicitly correlated to the nuclear orbital is implemented using a restricted open-shell formalism for these electrons. This method is applied to HCN + , and the nuclear densities are in qualitative agreement with grid-based calculations. Future work will focus on the significance of nonadiabatic effects in molecular systems and the further enhancement of the NEO-RXCHF approach to accurately describe such effects

Nuclear-electronic orbital reduced explicitly correlated Hartree-Fock approach: Restricted basis sets and open-shell systems

Energy Technology Data Exchange (ETDEWEB)

Brorsen, Kurt R.; Sirjoosingh, Andrew; Pak, Michael V.; Hammes-Schiffer, Sharon, E-mail: shs3@illinois.edu [Department of Chemistry, University of Illinois at Urbana-Champaign, 600 South Mathews Ave., Urbana, Illinois 61801 (United States)

2015-06-07

The nuclear electronic orbital (NEO) reduced explicitly correlated Hartree-Fock (RXCHF) approach couples select electronic orbitals to the nuclear orbital via Gaussian-type geminal functions. This approach is extended to enable the use of a restricted basis set for the explicitly correlated electronic orbitals and an open-shell treatment for the other electronic orbitals. The working equations are derived and the implementation is discussed for both extensions. The RXCHF method with a restricted basis set is applied to HCN and FHF{sup −} and is shown to agree quantitatively with results from RXCHF calculations with a full basis set. The number of many-particle integrals that must be calculated for these two molecules is reduced by over an order of magnitude with essentially no loss in accuracy, and the reduction factor will increase substantially for larger systems. Typically, the computational cost of RXCHF calculations with restricted basis sets will scale in terms of the number of basis functions centered on the quantum nucleus and the covalently bonded neighbor(s). In addition, the RXCHF method with an odd number of electrons that are not explicitly correlated to the nuclear orbital is implemented using a restricted open-shell formalism for these electrons. This method is applied to HCN{sup +}, and the nuclear densities are in qualitative agreement with grid-based calculations. Future work will focus on the significance of nonadiabatic effects in molecular systems and the further enhancement of the NEO-RXCHF approach to accurately describe such effects.

Analytic energy derivatives for the calculation of the first-order molecular properties using the domain-based local pair-natural orbital coupled-cluster theory

Science.gov (United States)

Datta, Dipayan; Kossmann, Simone; Neese, Frank

2016-09-01

The domain-based local pair-natural orbital coupled-cluster (DLPNO-CC) theory has recently emerged as an efficient and powerful quantum-chemical method for the calculation of energies of molecules comprised of several hundred atoms. It has been demonstrated that the DLPNO-CC approach attains the accuracy of a standard canonical coupled-cluster calculation to about 99.9% of the basis set correlation energy while realizing linear scaling of the computational cost with respect to system size. This is achieved by combining (a) localized occupied orbitals, (b) large virtual orbital correlation domains spanned by the projected atomic orbitals (PAOs), and (c) compaction of the virtual space through a truncated pair natural orbital (PNO) basis. In this paper, we report on the implementation of an analytic scheme for the calculation of the first derivatives of the DLPNO-CC energy for basis set independent perturbations within the singles and doubles approximation (DLPNO-CCSD) for closed-shell molecules. Perturbation-independent one-particle density matrices have been implemented in order to account for the response of the CC wave function to the external perturbation. Orbital-relaxation effects due to external perturbation are not taken into account in the current implementation. We investigate in detail the dependence of the computed first-order electrical properties (e.g., dipole moment) on the three major truncation parameters used in a DLPNO-CC calculation, namely, the natural orbital occupation number cutoff used for the construction of the PNOs, the weak electron-pair cutoff, and the domain size cutoff. No additional truncation parameter has been introduced for property calculation. We present benchmark calculations on dipole moments for a set of 10 molecules consisting of 20-40 atoms. We demonstrate that 98%-99% accuracy relative to the canonical CCSD results can be consistently achieved in these calculations. However, this comes with the price of tightening the

Photoabsorption of the molecular IH cation at the iodine 3 d absorption edge

Science.gov (United States)

Klumpp, Stephan; Guda, Alexander A.; Schubert, Kaja; Mertens, Karolin; Hellhund, Jonas; Müller, Alfred; Schippers, Stefan; Bari, Sadia; Martins, Michael

2018-03-01

Yields of atomic iodine Iq + (q ≥2 ) fragments resulting from photoexcitation and photoionization of the target ions IH+ and I+ have been measured in the photon-energy range 610-680 eV, which comprises the thresholds for iodine 3 d ionization. The measured ion-yield spectra show two strong and broad resonance features due to the excitation of the 3 d3 /2 ,5 /2 electrons into ɛ f states rather similar for both parent ions. In the 3 d pre-edge range, excitations into (n p π ) -like orbitals and into an additional σ* orbital are found for IH+, which have been identified by comparison of the atomic I+ and molecular IH+ data and with the help of (time-dependent) density functional theory (DFT) and atomic Hartree-Fock calculations. The (5 p π ) orbital is almost atomlike, whereas all other resonances of the IH+ primary ion show a more pronounced molecular character, which is deduced from the chemical shifts of the resonances and the theoretical analysis.

A case report of orbital Langerhans cell histiocytosis presenting as a orbital cellulitis.

Science.gov (United States)

Albert-Fort, M; González-Candial, M

2018-04-08

A 10-year-old girl was seen with a 3-week history of right upper lid swelling and with no other symptoms or fever. There was no recent history of sinusitis, trauma, or previous infection involving the periorbital area, or response to oral antibiotic treatment. Orbital computed tomography showed a lesion involving the upper margin of the orbit, and bone destruction at the orbital roof. Biopsy performed revealed the presence of Langerhans cell Histiocytosis. The lesion was surgically debulked and corticosteroids were used intra-operatively. The lesion responded to treatment. The orbital involvement of Langerhans cell histiocytosis, despite its low incidence, should be considered in the examination of acute peri-orbital swelling. It usually presents as an osteolytic lesion, and it is confirmed with a histological examination and immunohistochemical techniques for CD1a and S100. An interdisciplinary approach is recommended to rule out multifocal or multisystemic diseases, as well as to develop an appropriate treatment strategy. Copyright © 2018 Sociedad Española de Oftalmología. Publicado por Elsevier España, S.L.U. All rights reserved.

Quantitative evaluation of orbital hybridization in carbon nanotubes under radial deformation using π-orbital axis vector

Directory of Open Access Journals (Sweden)

Masato Ohnishi

2015-04-01

Full Text Available When a radial strain is applied to a carbon nanotube (CNT, the increase in local curvature induces orbital hybridization. The effect of the curvature-induced orbital hybridization on the electronic properties of CNTs, however, has not been evaluated quantitatively. In this study, the strength of orbital hybridization in CNTs under homogeneous radial strain was evaluated quantitatively. Our analyses revealed the detailed procedure of the change in electronic structure of CNTs. In addition, the dihedral angle, the angle between π-orbital axis vectors of adjacent atoms, was found to effectively predict the strength of local orbital hybridization in deformed CNTs.

The conservation of orbital symmetry

CERN Document Server

Woodward, R B

2013-01-01

The Conservation of Orbital Symmetry examines the principle of conservation of orbital symmetry and its use. The central content of the principle was that reactions occur readily when there is congruence between orbital symmetry characteristics of reactants and products, and only with difficulty when that congruence does not obtain-or to put it more succinctly, orbital symmetry is conserved in concerted reaction. This principle is expected to endure, whatever the language in which it may be couched, or whatever greater precision may be developed in its application and extension. The book ope

Similarity in Bilateral Isolated Internal Orbital Fractures.

Science.gov (United States)

Chen, Hung-Chang; Cox, Jacob T; Sanyal, Abanti; Mahoney, Nicholas R

2018-04-13

In evaluating patients sustaining bilateral isolated internal orbital fractures, the authors have observed both similar fracture locations and also similar expansion of orbital volumes. In this study, we aim to investigate if there is a propensity for the 2 orbits to fracture in symmetrically similar patterns when sustaining similar trauma. A retrospective chart review was performed studying all cases at our institution of bilateral isolated internal orbital fractures involving the medial wall and/or the floor at the time of presentation. The similarity of the bilateral fracture locations was evaluated using the Fisher's exact test. The bilateral expanded orbital volumes were analyzed using the Wilcoxon signed-rank test to assess for orbital volume similarity. Twenty-four patients with bilateral internal orbital fractures were analyzed for fracture location similarity. Seventeen patients (70.8%) had 100% concordance in the orbital subregion fractured, and the association between the right and the left orbital fracture subregion locations was statistically significant (P < 0.0001). Fifteen patients were analyzed for orbital volume similarity. The average orbital cavity volume was 31.2 ± 3.8 cm on the right and 32.0 ± 3.7 cm on the left. There was a statistically significant difference between right and left orbital cavity volumes (P = 0.0026). The data from this study suggest that an individual who suffers isolated bilateral internal orbital fractures has a statistically significant similarity in the location of their orbital fractures. However, there does not appear to be statistically significant similarity in the expansion of the orbital volumes in these patients.

Orbital Debris and NASA's Measurement Program

Science.gov (United States)

Africano, J. L.; Stansbery, E. G.

2002-05-01

Since the launch of Sputnik in 1957, the number of manmade objects in orbit around the Earth has dramatically increased. The United States Space Surveillance Network (SSN) tracks and maintains orbits on over nine thousand objects down to a limiting diameter of about ten centimeters. Unfortunately, active spacecraft are only a small percentage ( ~ 7%) of this population. The rest of the population is orbital debris or ``space junk" consisting of expended rocket bodies, dead payloads, bits and pieces from satellite launches, and fragments from satellite breakups. The number of these smaller orbital debris objects increases rapidly with decreasing size. It is estimated that there are at least 130,000 orbital debris objects between one and ten centimeters in diameter. Most objects smaller than 10 centimeters go untracked! As the orbital debris population grows, the risk to other orbiting objects, most importantly manned space vehicles, of a collision with a piece of debris also grows. The kinetic energy of a solid 1 cm aluminum sphere traveling at an orbital velocity of 10 km/sec is equivalent to a 400 lb. safe traveling at 60 mph. Fortunately, the volume of space in which the orbiting population resides is large, collisions are infrequent, but they do occur. The Space Shuttle often returns to earth with its windshield pocked with small pits or craters caused by collisions with very small, sub-millimeter-size pieces of debris (paint flakes, particles from solid rocket exhaust, etc.), and micrometeoroids. To get a more complete picture of the orbital-debris environment, NASA has been using both radar and optical techniques to monitor the orbital debris environment. This paper gives an overview of the orbital debris environment and NASA's measurement program.

Orbital structure in oscillating galactic potentials

Science.gov (United States)

Terzić, Balša; Kandrup, Henry E.

2004-01-01

Subjecting a galactic potential to (possibly damped) nearly periodic, time-dependent variations can lead to large numbers of chaotic orbits experiencing systematic changes in energy, and the resulting chaotic phase mixing could play an important role in explaining such phenomena as violent relaxation. This paper focuses on the simplest case of spherically symmetric potentials subjected to strictly periodic driving with the aim of understanding precisely why orbits become chaotic and under what circumstances they will exhibit systematic changes in energy. Four unperturbed potentials V0(r) were considered, each subjected to a time dependence of the form V(r, t) =V0(r)(1 +m0 sinωt). In each case, the orbits divide clearly into regular and chaotic, distinctions which appear absolute. In particular, transitions from regularity to chaos are seemingly impossible. Over finite time intervals, chaotic orbits subdivide into what can be termed `sticky' chaotic orbits, which exhibit no large-scale secular changes in energy and remain trapped in the phase-space region where they started; and `wildly' chaotic orbits, which do exhibit systematic drifts in energy as the orbits diffuse to different phase-space regions. This latter distinction is not absolute, transitions corresponding apparently to orbits penetrating a `leaky' phase-space barrier. The three different orbit types can be identified simply in terms of the frequencies for which their Fourier spectra have the most power. An examination of the statistical properties of orbit ensembles as a function of driving frequency ω allows us to identify the specific resonances that determine orbital structure. Attention focuses also on how, for fixed amplitude m0, such quantities as the mean energy shift, the relative measure of chaotic orbits and the mean value of the largest Lyapunov exponent vary with driving frequency ω and how, for fixed ω, the same quantities depend on m0.

Orbital roof encephalocele mimicking a destructive neoplasm.

Science.gov (United States)

Alsuhaibani, Adel H; Hitchon, Patrick W; Smoker, Wendy R K; Lee, Andrew G; Nerad, Jeffrey A

2011-01-01

The purpose of this case report is to report an orbital roof encephalocele mimicking a destructive orbital neoplasm. Orbital roof encephalocele is uncommon but can mimic neoplasm. One potential mechanism for the orbital roof destruction is a post-traumatic "growing orbital roof fracture." The growing fracture has been reported mostly in children but can occur in adults. Alternative potential etiologies for the encephalocele are discussed, including Gorham syndrome. Orbital roof encephalocele is uncommon in adults, and the findings can superficially resemble an orbital neoplasm. Radiographic and clinical features that might suggest the correct diagnosis include a prior history of trauma, overlying frontal lobe encephalomalacia without significant mass effect or edema, and an orbital roof defect. The "growing fracture" mechanism may be a potential explanation for the orbital roof destruction in some cases.

The globe and orbit in Laron syndrome.

Science.gov (United States)

Kornreich, L; Konen, O; Lilos, P; Laron, Z

2011-09-01

Patients with LS have an inborn growth hormone resistance, resulting in failure to generate IGF-1. The purpose of this study was to evaluate the size of the eye and orbit in LS. We retrospectively reviewed the MR imaging of the brain in 9 patients with LS for the following parameters: axial diameter of the globe, interzygomatic distance, perpendicular distance from the interzygomatic line to margins of the globe, medial-to-lateral diameter of the orbit at the anterior orbital rim, distance from the anterior orbital rim to the anterior globe, maximal distance between the medial walls of the orbits, lateral orbital wall angle, lateral orbital wall length, and mediolateral thickness of the intraorbital fat in the most cranial image of the orbit. All measurements were made bilaterally. Twenty patients referred for MR imaging for unrelated reasons served as control subjects. Compared with the control group, the patients with LS had a significantly smaller maximal globe diameter and shallower but wider orbits due to a shorter lateral wall, a smaller medial distance between the orbits, and a larger angle of the orbit. The ratio between the most anterior orbital diameter and the globe was greater than that in controls. The position of the globe was more anterior in relation to the interzygomatic line. Shallow and wide orbits and small globes relative to orbital size are seen in LS and may be secondary to IGF-1 deficiency.

Orbiting compressor for residential air-conditioners

Energy Technology Data Exchange (ETDEWEB)

Kim, Hyun Jin; Kim, Woo Young; Ahn, Jong Min [Department of Mechanical Engineering, University of Incheon, 12-1 Songdo-dong, Yeonsu-gu, Incheon 406-840 (Korea)

2010-01-15

A new type of compressor, called an orbiting compressor, is introduced in this paper. The orbiting compressor is characterized by an orbiting piston, and the piston or orbiter consists of a circular base plate and a ring type vane protruding vertically from the base plate. The orbiter is made to orbit in an annular space formed between two concentric circular walls via an Oldham-ring mechanism, producing two sealed gas pockets on both sides of the vane wrap with a 180 phase difference. This operating mechanism leads to alternating compression and discharge processes, which results in low torque variation. The orbiting compressor has been designed for an R410A residential air conditioner with a cooling capacity of 10.0 kW. The performance of the orbiting compressor model has been analytically investigated, where the volumetric, adiabatic and mechanical efficiencies were calculated to be 94.8%, 90.4% and 93.4%, respectively for the ARI condition. The EER was estimated to be about 10.86 with a motor efficiency of 89%. (author)

Molecular structure, vibrational spectra, MEP, HOMO-LUMO and NBO analysis of Hf(SeO3)(SeO4)(H2O)4

Science.gov (United States)

Yankova, Rumyana; Genieva, Svetlana; Halachev, Nenko; Dimitrova, Ginka

2016-02-01

Hf(SeO3)(SeO4)(H2O)4 was obtained with the hydrothermal synthesis. The geometry optimization of this molecule was done by Density Functional Theory (DFT/B3LYP) method with 6-31G(d) basis set and LANL2DZ for Hf. The experimental infrared spectrum was compared with calculated and complete vibrational assignment was provided. The bond orders and the electronic properties of the molecule were calculated. The natural bond orbital analysis (NBO) was performed in order to study the intramolecular bonding interactions among bonds and delocalization of unpaired electrons. The calculated highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) with frontier orbital gap were presented. The electrostatic potential was calculated in order to investigate the reaction properties of the molecule. The thermodynamic properties of the studied compound at different temperatures were calculated.

On the relation between orbital-localization and self-interaction errors in the density functional theory treatment of organic semiconductors.

Science.gov (United States)

Körzdörfer, T

2011-03-07

It is commonly argued that the self-interaction error (SIE) inherent in semilocal density functionals is related to the degree of the electronic localization. Yet at the same time there exists a latent ambiguity in the definitions of the terms "localization" and "self-interaction," which ultimately prevents a clear and readily accessible quantification of this relationship. This problem is particularly pressing for organic semiconductor molecules, in which delocalized molecular orbitals typically alternate with localized ones, thus leading to major distortions in the eigenvalue spectra. This paper discusses the relation between localization and SIEs in organic semiconductors in detail. Its findings provide further insights into the SIE in the orbital energies and yield a new perspective on the failure of self-interaction corrections that identify delocalized orbital densities with electrons. © 2011 American Institute of Physics.

Applicability of meteor radiant determination methods depending on orbit type. I. High-eccentric orbits

Science.gov (United States)

Svoren, J.; Neslusan, L.; Porubcan, V.

1993-07-01

It is evident that there is no uniform method of calculating meteor radiants which would yield reliable results for all types of cometary orbits. In the present paper an analysis of this problem is presented, together with recommended methods for various types of orbits. Some additional methods resulting from mathematical modelling are presented and discussed together with Porter's, Steel-Baggaley's and Hasegawa's methods. In order to be able to compare how suitable the application of the individual radiant determination methods is, it is necessary to determine the accuracy with which they approximate real meteor orbits. To verify the accuracy with which the orbit of a meteoroid with at least one node at 1 AU fits the original orbit of the parent body, we applied the Southworth-Hawkins D-criterion (Southworth, R.B., Hawkins, G.S.: 1963, Smithson. Contr. Astrophys 7, 261). D0.2 the fit is rather poor and the change of orbit unrealistic. The optimal methods with the smallest values of D for given types of orbits are shown in two series of six plots. The new method of rotation around the line of apsides we propose is very appropriate in the region of small inclinations. There is no doubt that Hasegawa's omega-adjustment method (Hasegawa, I.: 1990, Publ. Astron. Soc. Japan 42, 175) has the widest application. A comparison of the theoretical radiants with the observed radiants of seven known meteor showers is also presented.

Use of density functional theory orbitals in the GVVPT2 variant of second-order multistate multireference perturbation theory.

Science.gov (United States)

Hoffmann, Mark R; Helgaker, Trygve

2015-03-05

A new variation of the second-order generalized van Vleck perturbation theory (GVVPT2) for molecular electronic structure is suggested. In contrast to the established procedure, in which CASSCF or MCSCF orbitals are first obtained and subsequently used to define a many-electron model (or reference) space, the use of an orbital space obtained from the local density approximation (LDA) variant of density functional theory is considered. Through a final, noniterative diagonalization of an average Fock matrix within orbital subspaces, quasicanonical orbitals that are otherwise indistinguishable from quasicanonical orbitals obtained from a CASSCF or MCSCF calculation are obtained. Consequently, all advantages of the GVVPT2 method are retained, including use of macroconfigurations to define incomplete active spaces and rigorous avoidance of intruder states. The suggested variant is vetted on three well-known model problems: the symmetric stretching of the O-H bonds in water, the dissociation of N2, and the stretching of ground and excited states C2 to more than twice the equilibrium bond length of the ground state. It is observed that the LDA-based GVVPT2 calculations yield good results, of comparable quality to conventional CASSCF-based calculations. This is true even for the C2 model problem, in which the orbital space for each state was defined by the LDA orbitals. These results suggest that GVVPT2 can be applied to much larger problems than previously accessible.

Molecular structure, vibrational, UV, NMR, HOMO-LUMO, MEP, NLO, NBO analysis of 3,5 di tert butyl 4 hydroxy benzoic acid

Science.gov (United States)

Mathammal, R.; Sangeetha, K.; Sangeetha, M.; Mekala, R.; Gadheeja, S.

2016-09-01

In this study, we report a combined experimental and theoretical study on molecular structure and vibrational spectra of 3,5 di tert butyl 4 hydroxy benzoic acid. The properties of title compound have been evaluated by quantum chemical calculation (DFT) using B3LYP functional and 6-31 + G (d, p) as basis set. IR Spectra has been recorded using Fourier transform infrared spectroscopy (FT-IR) in the region 4000-400 cm-1. The vibrational assignment of the calculated normal modes has been made on the basis set. The isotropic chemical shifts computed by 13C and 1H NMR (Nuclear Magnetic Resonance) analyses also show good agreement with experimental observations. The theoretical UV-Vis spectrum of the compound are used to study the visible absorption maxima (λ max). The structure activity relationship have been interpreted by mapping electrostatic potential surface (MEP), which is valuable information for the quality control of medicines and drug receptor interactions. The Mullikan charges, HOMO (Highest Occupied Molecular Orbital) - LUMO (Lowest Unoccupied Molecular Orbital) energy are analyzed. HOMO-LUMO energy gap and other related molecular properties are also calculated. The Natural Bond Orbital (NBO) analysis is carried out to investigate the various intra and inter molecular interactions of molecular system. The Non-linear optical properties such as dipole moment (μ), polarizability (αtot) and molecular first order hyperpolarizability (β) of the title compound are computed with B3LYP/6-31 + G (d,p) level of theory.

Quark Orbital Angular Momentum

Directory of Open Access Journals (Sweden)

Burkardt Matthias

2015-01-01

Full Text Available Definitions of orbital angular momentum based on Wigner distributions are used as a framework to discuss the connection between the Ji definition of the quark orbital angular momentum and that of Jaffe and Manohar. We find that the difference between these two definitions can be interpreted as the change in the quark orbital angular momentum as it leaves the target in a DIS experiment. The mechanism responsible for that change is similar to the mechanism that causes transverse single-spin asymmetries in semi-inclusive deep-inelastic scattering.

Stellar orbits around Sgr A*

International Nuclear Information System (INIS)

Trippe, S; Gillessen, S; Ott, T; Eisenhauer, F; Paumard, T; Martins, F; Genzel, R; Schoedel, R; Eckart, A; Alexander, T

2006-01-01

In this article we present and discuss the latest results from the observations of stars (''S-stars'') orbiting Sgr A* . With improving data quality the number of observed S-stars has increased substantially in the last years. The combination of radial velocity and proper motion information allows an ever more precise determination of orbital parameters and of the mass of and the distance to the supermassive black hole in the centre of the Milky Way. Additionally, the orbital solutions allow us to verify an agreement between the NIR source Sgr A* and the dynamical centre of the stellar orbits to within 2 mas

Orbital and adnexal sarcoidosis

NARCIS (Netherlands)

Prabhakaran, Venkatesh C.; Saeed, Perooz; Esmaeli, Bita; Sullivan, Timothy J.; Mcnab, Alan; Davis, Garry; Valenzuela, Alejandra; Leibovitch, Igal; Kesler, Anat; Sivak-Callcott, Jennifer; Hoyama, Erika; Selva, Dinesh

2007-01-01

To present the clinical features and management in a series of patients with orbital and adnexal sarcoidosis. This multicenter retrospective study included patients with biopsy-proven noncaseating granuloma involving the orbit or adnexa and evidence of systemic sarcoidosis. Clinical records were

Comparative studies on molecular structure, vibrational spectra and hyperpolarizabilies of NLO chromophore Ethyl 4-Dimethylaminobenzoate

Science.gov (United States)

Amalanathan, M.; Jasmine, G. Femina; Roy, S. Dawn Dharma

2017-08-01

The molecular structure, vibrational spectra and polarizabilities of Ethyl 4-Dimethylaminobenzoate (EDAB) was investigated by density functional theory employing Becke's three parameter hybrid exchange functional with Lee-Yang-Parr (B3LYP) co-relational functional involving 6-311++G(d,p) basis set and compared with some other levels. A detailed interpretation of the IR and Raman spectra of EDBA have been reported and analyzed. Complete vibrational assignments of the vibrational modes have been done on the basis of the potential energy distribution (TED) using VEDA software. The molecular electrostatic potential mapped onto total density surface has been obtained. A study on the electronic properties, such as absorption wavelength, and frontier molecular orbitals energy, was performed using DFT approach. The stability of the molecule arising from hyper conjugative interactions and accompanying charge delocalization has been analyzed using natural bond orbital (NBO) analysis. The natural and Mulliken charge also calculated and compared with different level of calculation. The dipole moment, polarizability and first, second order hyperpolarizabilities of the title molecule were calculated and compared with the experimental values. The energy gap between frontier orbitals has been used along with electric moments and first order hyperpolarizability, to understand the non linear optical (NLO) activity of the molecule. The NLO activity of molecule was confirmed by SHG analysis.

Cosmic radiation monitoring at low-Earth orbit by means of thermoluminescence and plastic nuclear track detectors

Czech Academy of Sciences Publication Activity Database

Ambrožová, Iva; Pachnerová Brabcová, Kateřina; Kubančák, Ján; Šlegl, Jakub; Tolochek, R. V.; Ivanova, O. A.; Shurshakov, V. A.

2017-01-01

Roč. 106, č. 12 (2017), s. 262-266 ISSN 1350-4487 R&D Projects: GA ČR GJ15-16622Y Institutional support: RVO:61389005 Keywords : BION-M1 * cosmic radiation * low earth orbit * passive detector * thermoluminescent detector * plastic nuclear track detector Subject RIV: BG - Nuclear, Atomic and Molecular Physics, Colliders OBOR OECD: Nuclear physics Impact factor: 1.442, year: 2016

Molecular electronics--resonant transport through single molecules.

Science.gov (United States)

Lörtscher, Emanuel; Riel, Heike

2010-01-01

The mechanically controllable break-junction technique (MCBJ) enables us to investigate charge transport through an individually contacted and addressed molecule in ultra-high vacuum (UHV) environment at variable temperature ranging from room temperature down to 4 K. Using a statistical measurement and analysis approach, we acquire current-voltage (I-V) characteristics during the repeated formation, manipulation, and breaking of a molecular junction. At low temperatures, voltages accessing the first molecular orbitals in resonance can be applied, providing spectroscopic information about the junction's energy landscape, in particular about the molecular level alignment in respect to the Fermi energy of the electrodes. Thereby, we can investigate the non-linear transport properties of various types of functional molecules and explore their potential use as functional building blocks for future nano-electronics. An example will be given by the reversible and controllable switching between two distinct conductive states of a single molecule. As a proof-of-principle for functional molecular devices, a single-molecule memory element will be demonstrated.

Algorithms for orbit control on SPEAR

International Nuclear Information System (INIS)

Corbett, J.; Keeley, D.; Hettel, R.; Linscott, I.; Sebek, J.

1994-06-01

A global orbit feedback system has been installed on SPEAR to help stabilize the position of the photon beams. The orbit control algorithms depend on either harmonic reconstruction of the orbit or eigenvector decomposition. The orbit motion is corrected by dipole corrector kicks determined from the inverse corrector-to-bpm response matrix. This paper outlines features of these control algorithms as applied to SPEAR

Orbital Resonances in the Vinti Solution

Science.gov (United States)

Zurita, L. D.

As space becomes more congested, contested, and competitive, high-accuracy orbital predictions become critical for space operations. Current orbit propagators use the two-body solution with perturbations added, which have significant error growth when numerically integrated for long time periods. The Vinti Solution is a more accurate model than the two-body problem because it also accounts for the equatorial bulge of the Earth. Unfortunately, the Vinti solution contains small divisors near orbital resonances in the perturbative terms of the Hamiltonian, which lead to inaccurate orbital predictions. One approach to avoid the small divisors is to apply transformation theory, which is presented in this research. The methodology of this research is to identify the perturbative terms of the Vinti Solution, perform a coordinate transformation, and derive the new equations of motion for the Vinti system near orbital resonances. An analysis of these equations of motion offers insight into the dynamics found near orbital resonances. The analysis in this research focuses on the 2:1 resonance, which includes the Global Positioning System. The phase portrait of a nominal Global Positioning System satellite orbit is found to contain a libration region and a chaotic region. Further analysis shows that the dynamics of the 2:1 resonance affects orbits with semi-major axes ranging from -5.0 to +5.4 kilometers from an exactly 2:1 resonant orbit. Truth orbits of seven Global Positioning System satellites are produced for 10 years. Two of the satellites are found to be outside of the resonance region and three are found to be influenced by the libration dynamics of the resonance. The final satellite is found to be influenced by the chaotic dynamics of the resonance. This research provides a method of avoiding the small divisors found in the perturbative terms of the Vinti Solution near orbital resonances.

A Study of Electrocyclic Reactions in a Molecular Junction

DEFF Research Database (Denmark)

Olsen, Stine Tetzschner; Nielsen, Mogens Brøndsted; Hansen, Thorsten

2017-01-01

must be in accordance to the orbital symmetry rules expressed by the Woodward-Hoffmann rules (when the electrodes do not significantly alter the molecular orbital appearances). We find these two requirements to be valid for the dianion of (1E,3Z,5E)-hexa-1,3,5-triene-1,6-diamine, and the Coulomb...... blockade diamonds were therefore modeled for this compound to elucidate how a dark photoswitching event would manifest itself in the stability plot. From this modeling of conductance as a function of gate and bias potentials, we predict a collapse in Coulomb diamond size, that is, a decrease in the height...

Orbit determination for ISRO satellite missions

Science.gov (United States)

Rao, Ch. Sreehari; Sinha, S. K.

Indian Space Research Organisation (ISRO) has been successful in using the in-house developed orbit determination and prediction software for satellite missions of Bhaskara, Rohini and APPLE. Considering the requirements of satellite missions, software packages are developed, tested and their accuracies are assessed. Orbit determination packages developed are SOIP, for low earth orbits of Bhaskara and Rohini missions, ORIGIN and ODPM, for orbits related to all phases of geo-stationary missions and SEGNIP, for drift and geo-stationary orbits. Software is tested and qualified using tracking data of SIGNE-3, D5-B, OTS, SYMPHONIE satellites with the help of software available with CNES, ESA and DFVLR. The results match well with those available from these agencies. These packages have supported orbit determination successfully throughout the mission life for all ISRO satellite missions. Member-Secretary

Thermochemistry of the reactions of PH +2 ( 1A 1) and PH +2 ( 3B 1) with CO. A G2 molecular orbital study

Science.gov (United States)

Esseffar, M.; Luna, A.; Mó, O.; Yáñez, M.

1994-06-01

The Gaussian-2 (G2) theoretical procedure, based on ab initio molecular orbital theory, is used to study the potential energy surfaces corresponding to gas phase reactions between PH +2 singlet and triplet state cations with carbon monoxide. Important differences between singlets and triplets, both regarding their bonding and their stabilities have been found. The most outstanding result is that, although the first 3B 1 excited state of PH +2 is only about 20 kcal/mol above the 1A 1 ground state, the singlet global minimum of the [H 2, P, C, O] + potential energy surface lies 61 kcal/mol below the triplet global minimum. This is so because, in general, triplet state cations are ion—dipole complexes, while the singlets are covalently bound species. In agreement with experimental evidence, only the formation of the adduct is exothermic, while all processes yielding PO or PC containing species as well as the proton transfer reaction, are strongly endothermic. Estimates of the heats of formation of H 2PO + and HCP species are given.

Space Tourism: Orbital Debris Considerations

Science.gov (United States)

Mahmoudian, N.; Shajiee, S.; Moghani, T.; Bahrami, M.

2002-01-01

Space activities after a phase of research and development, political competition and national prestige have entered an era of real commercialization. Remote sensing, earth observation, and communication are among the areas in which this growing industry is facing competition and declining government money. A project like International Space Station, which draws from public money, has not only opened a window of real multinational cooperation, but also changed space travel from a mere fantasy into a real world activity. Besides research activities for sending man to moon and Mars and other outer planets, space travel has attracted a considerable attention in recent years in the form of space tourism. Four countries from space fairing nations are actively involved in the development of space tourism. Even, nations which are either in early stages of space technology development or just beginning their space activities, have high ambitions in this area. This is worth noting considering their limited resources. At present, trips to space are available, but limited and expensive. To move beyond this point to generally available trips to orbit and week long stays in LEO, in orbital hotels, some of the required basic transportations, living requirements, and technological developments required for long stay in orbit are already underway. For tourism to develop to a real everyday business, not only the price has to come down to meaningful levels, but also safety considerations should be fully developed to attract travelers' trust. A serious hazard to space activities in general and space tourism in particular is space debris in earth orbit. Orbiting debris are man-made objects left over by space operations, hazardous to space missions. Since the higher density of debris population occurs in low earth orbit, which is also the same orbit of interest to space tourism, a careful attention should be paid to the effect of debris on tourism activities. In this study, after a

Design strategies for organic semiconductors beyond the molecular formula.

Science.gov (United States)

Henson, Zachary B; Müllen, Klaus; Bazan, Guillermo C

2012-09-01

Organic semiconducting materials based on polymers and molecular systems containing an electronically delocalized structure are the basis of emerging optoelectronic technologies such as plastic solar cells and flexible transistors. For isolated molecules, guidelines exist that rely on the molecular formula to tailor the frontier (highest occupied or lowest unoccupied) molecular orbital energy levels and optical absorption profiles. Much less control can be achieved over relevant properties, however, as one makes the transition to the ensemble behaviour characteristic of the solid state. Polymeric materials are also challenging owing to the statistical description of the average number of repeat units. Here we draw attention to the limitations of molecular formulae as predictive tools for achieving properties relevant to device performances. Illustrative examples highlight the relevance of organization across multiple length scales, and how device performances--although relevant for practical applications--poorly reflect the success of molecular design.

Thrombosis of orbital varices

International Nuclear Information System (INIS)

Boschi Oyhenart, J.; Tenyi, A.; Boschi Pau, J.

2002-01-01

Orbital varices are venous malformations produced by an abnormal dilatation of one or more orbital veins, probably associated with congenital weakness of the vascular wall. They are rare lesions, usually occurring in young patients, that produce intermittent proptosis related to the increase in the systemic venous pressure. The presence of hemorrhage or thrombosis is associated with rapid development of proptosis, pain and decreased ocular motility. We report the cases of two adult patients with orbital varices complicated by thrombosis in whom the diagnosis was based on computed tomography. The ultrasound and magnetic resonance findings are also discussed. (Author) 16 refs

Spatial analysis of galactic cosmic ray particles in low earth orbit/near equator orbit using SPENVIS

International Nuclear Information System (INIS)

Suparta, W; Zulkeple, S K

2014-01-01

The space environment has grown intensively harmful to spacecraft and astronauts. Galactic cosmic rays (GCRs) are one of the radiation sources that composed of high energetic particles originated from space and capable of damaging electronic systems through single event upset (SEU) process. In this paper, we analyzed GCR fluxes at different altitudes by using Space Environment Information System (SPENVIS) software and the results are compared to determine their intensities with respect to distance in the Earth's orbit. The altitudes are set at low earth orbit (400 km and 685 km), medium earth orbit (19,100 km and 20,200 km) and high earth orbit (35,793 km and 1,000,000 km). Then, within Low Earth Orbit (LEO) near the equator (NEqO), we used altitude of 685 km to compare GCRs with the intensities of solar particles and trapped particles in the radiation belt to determine the significance of GCRs in the orbit itself.

Orbital and Landing Operations at Near-Earth

Science.gov (United States)

Scheeres, D. J.

1995-01-01

Orbital and landing operations about near-Earth asteroids are different than classical orbital operations about large bodies. The major differences lie with the small mass of the asteroid, the lower orbital velocities, the larger Solar tide and radiation pressure perturbations, the irregular shape of the asteroid and the potential for non-uniform rotation of the asteroid. These differences change the nature of orbits about an asteroid to where it is often common to find trajectories that evolve from stable, near-circular orbits to crashing or escaping orbits in a matter of days. The understanding and control of such orbits is important if a human or robotic presence at asteroids is to be commonplace in the future.

Metrics in Keplerian orbits quotient spaces

Science.gov (United States)

Milanov, Danila V.

2018-03-01

Quotient spaces of Keplerian orbits are important instruments for the modelling of orbit samples of celestial bodies on a large time span. We suppose that variations of the orbital eccentricities, inclinations and semi-major axes remain sufficiently small, while arbitrary perturbations are allowed for the arguments of pericentres or longitudes of the nodes, or both. The distance between orbits or their images in quotient spaces serves as a numerical criterion for such problems of Celestial Mechanics as search for common origin of meteoroid streams, comets, and asteroids, asteroid families identification, and others. In this paper, we consider quotient sets of the non-rectilinear Keplerian orbits space H. Their elements are identified irrespective of the values of pericentre arguments or node longitudes. We prove that distance functions on the quotient sets, introduced in Kholshevnikov et al. (Mon Not R Astron Soc 462:2275-2283, 2016), satisfy metric space axioms and discuss theoretical and practical importance of this result. Isometric embeddings of the quotient spaces into R^n, and a space of compact subsets of H with Hausdorff metric are constructed. The Euclidean representations of the orbits spaces find its applications in a problem of orbit averaging and computational algorithms specific to Euclidean space. We also explore completions of H and its quotient spaces with respect to corresponding metrics and establish a relation between elements of the extended spaces and rectilinear trajectories. Distance between an orbit and subsets of elliptic and hyperbolic orbits is calculated. This quantity provides an upper bound for the metric value in a problem of close orbits identification. Finally the invariance of the equivalence relations in H under coordinates change is discussed.

Posttraumatic Orbital Emphysema: A Numerical Model

Directory of Open Access Journals (Sweden)

Andrzej Skorek

2014-01-01

Full Text Available Orbital emphysema is a common symptom accompanying orbital fracture. The pathomechanism is still not recognized and the usually assumed cause, elevated pressure in the upper airways connected with sneezing or coughing, does not always contribute to the occurrence of this type of fracture. Observations based on the finite model (simulating blowout type fracture of the deformations of the inferior orbital wall after a strike in its lower rim. Authors created a computer numeric model of the orbit with specified features—thickness and resilience modulus. During simulation an evenly spread 14400 N force was applied to the nodular points in the inferior rim (the maximal value not causing cracking of the outer rim, but only ruptures in the inferior wall. The observation was made from 1·10-3 to 1·10-2 second after a strike. Right after a strike dislocations of the inferior orbital wall toward the maxillary sinus were observed. Afterwards a retrograde wave of the dislocation of the inferior wall toward the orbit was noticed. Overall dislocation amplitude reached about 6 mm. Based on a numeric model of the orbit submitted to a strike in the inferior wall an existence of a retrograde shock wave causing orbital emphysema has been found.

Matrix isolation FT-IR spectroscopy and molecular orbital study of sarcosine methyl ester

Science.gov (United States)

Gómez-Zavaglia, A.; Fausto, R.

2004-02-01

N-methylglycine methyl ester (sarcosine-Me) has been studied by matrix isolation FT-IR spectroscopy and molecular orbital calculations undertaken at the DFT/B3LYP and MP2 levels of theory with the 6-311++G(d,p) and 6-31++G(d,p) basis set, respectively. Twelve different conformers were located in the potential energy surface of the studied compound, with the ASC conformer being the ground conformational state. This form is analogous to the dimethylglycine methyl ester most stable conformer and is characterized by a NH⋯O intramolecular hydrogen bond; in this form, the ester group assumes the cis configuration and the OC-C-N and Lp-N-C-C (where Lp is the nitrogen lone electron pair) dihedral angles are ca. -17.8 and 171.3°, respectively. The second most stable conformer ( GSC) differs from the ASC conformer essentially in the conformation assumed by the methylamino group, which in this case is gauche ( Lp-N-C-C dihedral angle equal to 79.4°). On the other hand, the third most stable conformer ( AAC) differs from the most stable form in the conformation of the OC-C-N axis (151.4°). These three forms were predicted to differ in energy by less than ca. 5 kJ mol -1 and represent ≈95% of the total conformational population at room temperature. FT-IR spectra were obtained for sarcosine-Me isolated in argon matrices (T=9 K) revealing the presence in the matrices of the three lowest energy conformers predicted by the calculations. The matrices were prepared by deposition of the vapour of the compound using two different nozzle temperatures, 25 and 60 °C. The relative populations of the three conformers trapped in the matrices were found to be consistent with occurrence of conformational cooling during matrix deposition and with a stabilization of the most polar GSC and AAC conformers in the matrices compared to the gas phase. Indeed, like it was previously observed for the methyl ester of dimethylglycine [Phys. Chem. Chem. Phys. 5 (2003) 52] the different

Hemangiopericitoma de órbita Orbital hemangiopericytoma

Directory of Open Access Journals (Sweden)

Ana Paula Ximenes Alves

2001-04-01

Full Text Available Objetivo: Descrever um raro caso de hemangiopericitoma orbital. Métodos: Relato de caso de associação entre hemangipericitoma orbital e blefaroptose. Resultados: A exérese da neoplasia normalizou o posicionamento palpebral. Conclusões: Lesões orbitais anteriores são causas de blefaroptose por compressão do músculo elevador palpebral.Purpose: To describe a rare case of orbital hemangiope- ricytoma. Methods: Case report of an association of blepha-roptosis with orbital hemangiopericytoma. Results: When the lesion was surgically removed the position of the upper eyelid returned to normal. Conclusions: Anterior orbital lesions can lead to blepharoptosis by compression of the levator palpebrae muscle.

Failure of single electron descriptions of molecular orbital collision processes

International Nuclear Information System (INIS)

Elston, S.B.

1978-01-01

Inner-shell excitation occurring in low and moderate (keV range) energy collisions between light atomic and ionic systems is frequently describable in terms of molecular promotion mechanisms, which were extensively explored both theoretically and experimentally. The bulk of such studies have concentrated on processes understandable through the use of single- and independent-electron models. Nonetheless, it is possible to find cases of inner-shell excitation in relatively simple collision systems which involve nearly simultaneous multiple-electron transitions and transitions induced by inherently two-electron interactions. Evidence for these many- and nonindependent-electron phenomena in inner-shell excitation processes and the importance of considering such effects in the interpretation of collisionally induced excitation spectra is discussed. 13 references

Theory and design methods of special space orbits

CERN Document Server

Zhang, Yasheng; Zhou, Haijun

2017-01-01

This book focuses on the theory and design of special space orbits. Offering a systematic and detailed introduction to the hovering orbit, spiral cruising orbit, multi-target rendezvous orbit, initiative approaching orbit, responsive orbit and earth pole-sitter orbit, it also discusses the concept, theory, design methods and application of special space orbits, particularly the design and control method based on kinematics and astrodynamics. In addition the book presents the latest research and its application in space missions. It is intended for researchers, engineers and postgraduates, especially those working in the fields of orbit design and control, as well as space-mission planning and research.

On the lunar node resonance of the orbital plane evolution of the Earth's satellite orbits

Science.gov (United States)

Zhu, Ting-Lei

2018-06-01

This paper aims to investigate the effects of lunar node resonance on the circular medium Earth orbits (MEO). The dynamical model is established in classical Hamiltonian systems with the application of Lie transform to remove the non-resonant terms. Resonant condition, stability and phase structures are studied. The lunar node resonance occurs when the secular changing rates of the orbital node (with respect to the equator) and the lunar node (with respect to the ecliptic) form a simple integer ratio. The resonant conditions are satisfied for both inclined and equatorial orbits. The orbital plane would have long period (with typical timescales of several centuries) fluctuation due to the resonance.

Meteoroid Orbits from Observations

Science.gov (United States)

Campbell-Brown, Margaret

2018-04-01

Millions of orbits of meteoroids have been measured over the last few decades, and they comprise the largest sample of orbits of solar system bodies which exists. The orbits of these objects can shed light on the distribution and evolution of comets and asteroids in near-Earth space (e.g. Neslusan et al. 2016). If orbits can be measured at sufficiently high resolution, individual meteoroids can be traced back to their parent bodies and, in principle, even to their ejection time (Rudawska et al. 2012). Orbits can be measured with multi-station optical observations or with radar observations.The most fundamental measured quantities are the speed of the meteor and the two angles of the radiant, or point in the sky from which the meteor appears to come. There are many methods used to determine these from observations, but not all produce the most accurate results (Egal et al. 2017). These three measured quantities, along with the time and location of the observation, are sufficient to obtain an orbit (see, e.g., Clark & Wiegert 2011), but the measurements must be corrected for the deceleration of the meteoroid in the atmosphere before it was detected, the rotation of the Earth, and the gravitational attraction of the Earth (including higher order moments if great precision is necessary).Once meteor orbits have been determined, studies of the age and origin of meteor showers (Bruzzone et al., 2015), the parent bodies of sporadic sources (Pokorny et al. 2014), and the dynamics of the meteoroid complex as a whole can be constrained.Bruzzone, J. S., Brown, P., Weryk, R., Campbell-Brown, M., 2015. MNRAS 446, 1625.Clark, D., Wiegert, P., 2011. M&PS 46, 1217.Egal, A., Gural, P., Vaubaillon, J., Colas, F., Thuillot, W., 2017. Icarus 294, 43.Neslusan, L., Vaubaillon, J., Hajdukova, M., 2016. A&A 589, id.A100.Pokorny, P., Vokrouhlicky, D., Nesvorny, D., Campbell-Brown, M., Brown, P., 2014. ApJ 789, id.25.Rudawska, R., Vaubaillon, J., Atreya, P., 2012. A&A 541, id.A2

Orbital Reconstruction: Patient-Specific Orbital Floor Reconstruction Using a Mirroring Technique and a Customized Titanium Mesh.

Science.gov (United States)

Tarsitano, Achille; Badiali, Giovanni; Pizzigallo, Angelo; Marchetti, Claudio

2016-10-01

Enophthalmos is a severe complication of primary reconstruction of orbital floor fractures. The goal of secondary reconstruction procedures is to restore symmetrical globe positions to recover function and aesthetics. The authors propose a new method of orbital floor reconstruction using a mirroring technique and a customized titanium mesh, printed using a direct metal laser-sintering method. This reconstructive protocol involves 4 steps: mirroring of the healthy orbit at the affected site, virtual design of a patient-specific orbital floor mesh, CAM procedures for direct laser-sintering of the customized titanium mesh, and surgical insertion of the device. Using a computed tomography data set, the normal, uninjured side of the craniofacial skeleton was reflected onto the contralateral injured side, and a reconstructive orbital floor mesh was designed virtually on the mirrored orbital bone surface. The solid-to-layer files of the mesh were then manufactured using direct metal laser sintering, which resolves the shaping and bending biases inherent in the indirect method. An intraoperative navigation system ensured accuracy of the entire procedure. Clinical outcomes were assessed using 3dMD photogrammetry and computed tomography data in 7 treated patients. The technique described here appears to be a viable method to correct complex orbital floor defects needing delayed reconstruction. This study represents the first step in the development of a wider experimental protocol for orbital floor reconstruction using computer-assisted design-computer-assisted manufacturing technology.

Spectroscopic investigations (FT-IR & FT-Raman) and molecular docking analysis of 6-[1-methyl-4-nitro-1H-imidazol-5-yl) sulfonyl]-7H-purine

Science.gov (United States)

Prasath, M.; Govindammal, M.; Sathya, B.

2017-10-01

The Azathioprine is used as anticancer agent. Azathioprine is chemically called 6-[1-methyl-4-nitro-1H-imidazol-5-yl) sulfonyl]-7H-purine (6M4N5P). The vibrational analysis of the 6M4N5P compound was carried out by using FT-IR and FT-Raman spectroscopic techniques and compared with aspects. The optimized geometry, frequency and intensity of the vibrational bands of 6M4N5P were obtained from the HF and DFT methods with 6-31G (d,p) basis set. The harmonic vibrational frequencies were calculated and the scaled values have been compared with experimental FT-IR and FT-Raman spectra. The calculated Highest Occupied Molecular Orbital (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO) energies show that charge transfer occur within the molecule. MEP (Molecular Electrostatic Potential) is very useful in the investigation of the charge distributions and molecular structure. The molecule orbital contributions were determined by using the total density of states (TDOS). A molecular docking analysis has been carried out to understand the conformational change and electrostatic properties of 6M4N5P in the active site of Rac1-Receptor.

Cost Per Pound From Orbit

Science.gov (United States)

Merriam, M. L.

2002-01-01

Traditional studies of Reusable Launch Vehicle (RLV) designs have focused on designs that are completely reusable except for the fuel. This may not be realistic with current technology . An alternate approach is to look at partially reusable launch vehicles. This raises the question of which parts should be reused and which parts should be expendable. One approach is to consider the cost/pound of returning these parts from orbit. With the shuttle, this cost is about three times the cost/pound of launching payload into orbit. A subtle corollary is that RLVs are much less practical for higher orbits, such as the one on which the International Space Station resides, than they are for low earth orbits.

Many-body theory of electrical, thermal and optical response of molecular heterojunctions

Science.gov (United States)

Bergfield, Justin Phillip

In this work, we develop a many-body theory of electronic transport through single molecule junctions based on nonequilibrium Green's functions (NEGFs). The central quantity of this theory is the Coulomb self-energy matrix of the junction SigmaC. SigmaC is evaluated exactly in the sequential-tunneling limit, and the correction due to finite lead-molecule tunneling is evaluated using a conserving approximation based on diagrammatic perturbation theory on the Keldysh contour. In this way, tunneling processes are included to infinite order, meaning that any approximation utilized is a truncation in the physical processes considered rather than in the order of those processes. Our theory reproduces the key features of both the Coulomb blockade and coherent transport regimes simultaneously in a single unified theory. Nonperturbative effects of intramolecular correlations are included, which are necessary to accurately describe the highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gap, essential for a quantitative theory of transport. This work covers four major topics related to transport in single-molecule junctions. First, we use our many-body theory to calculate the nonlinear electrical response of the archetypal Au-1,4-benzenedithiol-Au junction and find irregularly shaped 'molecular diamonds' which have been experimentally observed in some larger molecules but which are inaccessible to existing theoretical approaches. Next, we extend our theory to include heat transport and develop an exact expression for the heat current in an interacting nanostructure. Using this result, we discover that quantum coherence can strongly enhance the thermoelectric response of a device, a result with a number of technological applications. We then develop the formalism to include multi-orbital lead-molecule contacts and multi-channel leads, both of which strongly affect the observable transport. Lastly, we include a dynamic screening correction to

Modification of an impulse-factoring orbital transfer technique to account for orbit determination and maneuver execution errors

Science.gov (United States)

Kibler, J. F.; Green, R. N.; Young, G. R.; Kelly, M. G.

1974-01-01

A method has previously been developed to satisfy terminal rendezvous and intermediate timing constraints for planetary missions involving orbital operations. The method uses impulse factoring in which a two-impulse transfer is divided into three or four impulses which add one or two intermediate orbits. The periods of the intermediate orbits and the number of revolutions in each orbit are varied to satisfy timing constraints. Techniques are developed to retarget the orbital transfer in the presence of orbit-determination and maneuver-execution errors. Sample results indicate that the nominal transfer can be retargeted with little change in either the magnitude (Delta V) or location of the individual impulses. Additonally, the total Delta V required for the retargeted transfer is little different from that required for the nominal transfer. A digital computer program developed to implement the techniques is described.

The Carter constant for inclined orbits about a massive Kerr black hole: I. Circular orbits

Energy Technology Data Exchange (ETDEWEB)

Komorowski, P G; Valluri, S R; Houde, M, E-mail: pkomorow@uwo.c, E-mail: valluri@uwo.c, E-mail: mhoude2@uwo.c [Department of Physics and Astronomy, University of Western Ontario, London, Ontario (Canada)

2010-11-21

In an extreme binary black hole system, an orbit will increase its angle of inclination ({iota}) as it evolves in Kerr spacetime. We focus our attention on the behaviour of the Carter constant (Q) for near-polar orbits, and develop an analysis that is independent of and complements radiation-reaction models. For a Schwarzschild black hole, the polar orbits represent the abutment between the prograde and retrograde orbits at which Q is at its maximum value for given values of the latus rectum ({tilde l}) and the eccentricity (e). The introduction of spin ({tilde S}={vert_bar}J{vert_bar}/M{sup 2}) to the massive black hole causes this boundary, or abutment, to be moved towards greater orbital inclination; thus, it no longer cleanly separates prograde and retrograde orbits. To characterize the abutment of a Kerr black hole (KBH), we first investigated the last stable orbit (LSO) of a test-particle about a KBH, and then extended this work to general orbits. To develop a better understanding of the evolution of Q we developed analytical formulae for Q in terms of {tilde l}, e and {tilde S} to describe elliptical orbits at the abutment, polar orbits and LSOs. By knowing the analytical form of {partial_derivative}Q/{partial_derivative}{tilde l} at the abutment, we were able to test a 2PN flux equation for Q. We also used these formulae to numerically calculate the {partial_derivative}{iota}/{partial_derivative}{tilde l} of hypothetical circular orbits that evolve along the abutment. From these values we have determined that {partial_derivative}{iota}/{partial_derivative}{tilde l} = -(122.7{tilde S} - 36{tilde S}{sup 3}){tilde l}{sup -11/2} - (63/2 {tilde S} + 35/4 {tilde S}{sup 3}){tilde l}{sup -9/2} - 15/2 {tilde S}{tilde l}{sup -7/2} - 9/2 {tilde S}{tilde l}{sup -5/2}. By taking the limit of this equation for {tilde l} {yields} {infinity}, and comparing it with the published result for the weak-field radiation reaction, we found the upper limit on

Spin density and orbital optimization in open shell systems: A rational and computationally efficient proposal

Energy Technology Data Exchange (ETDEWEB)

Giner, Emmanuel, E-mail: gnrmnl@unife.it; Angeli, Celestino, E-mail: anc@unife.it [Dipartimento di Scienze Chimiche e Famaceutiche, Universita di Ferrara, Via Fossato di Mortara 17, I-44121 Ferrara (Italy)

2016-03-14

The present work describes a new method to compute accurate spin densities for open shell systems. The proposed approach follows two steps: first, it provides molecular orbitals which correctly take into account the spin delocalization; second, a proper CI treatment allows to account for the spin polarization effect while keeping a restricted formalism and avoiding spin contamination. The main idea of the optimization procedure is based on the orbital relaxation of the various charge transfer determinants responsible for the spin delocalization. The algorithm is tested and compared to other existing methods on a series of organic and inorganic open shell systems. The results reported here show that the new approach (almost black-box) provides accurate spin densities at a reasonable computational cost making it suitable for a systematic study of open shell systems.

Analysis of orbit determination from Earth-based tracking for relay satellites in a perturbed areostationary orbit

Science.gov (United States)

Romero, P.; Pablos, B.; Barderas, G.

2017-07-01

Areostationary satellites are considered a high interest group of satellites to satisfy the telecommunications needs of the foreseen missions to Mars. An areostationary satellite, in an areoequatorial circular orbit with a period of 1 Martian sidereal day, would orbit Mars remaining at a fixed location over the Martian surface, analogous to a geostationary satellite around the Earth. This work addresses an analysis of the perturbed orbital motion of an areostationary satellite as well as a preliminary analysis of the aerostationary orbit estimation accuracy based on Earth tracking observations. First, the models for the perturbations due to the Mars gravitational field, the gravitational attraction of the Sun and the Martian moons, Phobos and Deimos, and solar radiation pressure are described. Then, the observability from Earth including possible occultations by Mars of an areostationary satellite in a perturbed areosynchronous motion is analyzed. The results show that continuous Earth-based tracking is achievable using observations from the three NASA Deep Space Network Complexes in Madrid, Goldstone and Canberra in an occultation-free scenario. Finally, an analysis of the orbit determination accuracy is addressed considering several scenarios including discontinuous tracking schedules for different epochs and different areoestationary satellites. Simulations also allow to quantify the aerostationary orbit estimation accuracy for various tracking series durations and observed orbit arc-lengths.

Antenatal sonographic appearance of a large orbital encephalocele: a case report and differential diagnosis of orbital cystic mass.

Science.gov (United States)

Ahmed, Ahmed; Noureldin, Rehab; Gendy, Mohamed; Sakr, Sharif; Abdel Naby, Mahmoud

2013-06-01

Orbital meningoceles and encephaloceles are rare extracranial extensions of the brain and meninges with or without direct communication between the central nervous system and the abnormal mass. We reported a rare case of large fetal orbital encephalocele; the diagnosis was suspected initially by prenatal ultrasound and confirmed by postnatal MRI and CT scans. The differential diagnosis of an intrauterine fetal cystic orbital mass includes orbital teratoma, epidermoid inclusion cysts, hemangioma or lymphangioma, congenital cystic eye, dacryocystocele, and orbital cephalocele. Copyright © 2012 Wiley Periodicals, Inc.

Periodic orbits near the particle resonance in galaxies

CERN Document Server

Contopoulos, George

1978-01-01

Near the particle resonance of a spiral galaxy the almost circular periodic orbits that exist inside the resonance (direct) or outside it (retrograde) are replaced by elongated trapped orbits around the maxima of the potential L/sub 4/ and L/sub 5/. These are the long- period trapped periodic orbits. The long-period orbits shrink to the points L/sub 4/, L/sub 5/ for a critical value of the Hamiltonian h. For still larger h, a family of short-period trapped orbits appears, with continuously growing size. The evolution of the periodic orbits with h is followed, theoretically and numerically, from the untrapped orbits to the long-periodic orbits and then to the short-periodic orbits, mainly in the case of a bar. In a tight spiral case an explanation of the asymmetric periodic and banana orbits is given, and an example of short-period orbits not surrounding L/sub 4/ or L/sub 5/ is provided. Another family of periodic orbits reaching corotation is trapped at the inner Lindblad resonance. (5 refs).

European ST80 community-associated methicillin-resistant Staphylococcus aureus orbital cellulitis in a neonate

Directory of Open Access Journals (Sweden)

Tsironi Evangelia E

2012-05-01

Full Text Available Abstract Background Methicillin-resistant Staphylococcus aureus is a serious cause of morbidity and mortality in hospital environment, but also, lately, in the community. This case report is, to our knowledge, the first detailed description of a community-associated methicillin-resistant S. aureus ST80 orbital cellulitis in a previously healthy neonate. Possible predisposing factors of microbial acquisition and treatment selection are also discussed. Case presentation A 28-day-old Caucasian boy was referred to our hospital with the diagnosis of right orbital cellulitis. His symptoms included right eye proptosis, periocular edema and redness. Empirical therapy of intravenous daptomycin, rifampin and ceftriaxone was initiated. The culture of pus yielded a methicillin-resistant S. aureus isolate and the molecular analysis revealed that it was a Panton-Valentine leukocidine-positive ST80 strain. The combination antimicrobial therapy was continued for 42days and the infection was successfully controlled. Conclusions Clinicians should be aware that young infants, even without any predisposing condition, are susceptible to orbital cellulitis caused by community-associated methicillin-resistant S. aureus. Prompt initiation of the appropriate empirical therapy, according to the local epidemiology, should successfully address the infection, preventing ocular and systemic complications.

Vector properties in molecular photodissociation

International Nuclear Information System (INIS)

Underwood, J.

1999-12-01

The technique of resonance enhanced multi-photon ionization (REMPI) of atomic and molecular species produced from a photofragmentation event combined with time-of flight (TOF) detection is used to examine scalar and vector properties following photodissociation. This technique is applied to the study of methyl bromide dissociation in a product state specific manner. We report measurements of the angular distributions and kinetic energy releases of the resulting bromine atoms in the ground and first spin-orbit excited state. Additionally we report measurements of the angular distributions and kinetic energy releases of the methyl fragment in the ground vibrational state, and also the excited state with one quanta in the ν 2 vibrational modes. These studies were carried out in the red wing of the absorption band at several wavelengths. For these measurements we were able to resolve the spin orbit state of the partner bromine fragment. From our observations we find new evidence for enhanced nonadiabatic curve crossing active in methyl bromide dissociation in comparison with earlier studies of methyl iodide. The atomic polarization produced following photodissociation of a diatomic molecule was investigated both theoretically and experimentally. We develop theoretical expressions relating the lab frame and molecular frame atomic polarization to the photoexcitation and subsequent dissociation of a diatomic molecule. This treatment includes both incoherent, coherent and non-adiabatic processes which may be active in the photodissociation process. We treat the general case of a polarized diatomic molecule yielding two fragments with non zero angular momentum. Experimentally, an investigation of the polarization of atomic Cl( 2 P 3/2 ) photofragments from the ∼330 nm photolysis of molecular chlorine using the REMPI-TOF technique is reported. We present a theoretical framework in which to treat such experiments allowing the extraction of parameters with direct physical

Meta-orbital transition in heavy-fermion systems. Analysis by dynamical mean field theory and self-consistent renormalization theory of orbital fluctuations

International Nuclear Information System (INIS)

Hattori, Kazumasa

2010-01-01

We investigate a two-orbital Anderson lattice model with Ising orbital intersite exchange interactions on the basis of a dynamical mean field theory combined with the static mean field approximation of intersite orbital interactions. Focusing on Ce-based heavy-fermion compounds, we examine the orbital crossover between two orbital states, when the total f-electron number per site n f is ∼1. We show that a 'meta-orbital' transition, at which the occupancy of two orbitals changes steeply, occurs when the hybridization between the ground-state f-electron orbital and conduction electrons is smaller than that between the excited f-electron orbital and conduction electrons at low pressures. Near the meta-orbital critical end point, orbital fluctuations are enhanced and couple with charge fluctuations. A critical theory of meta-orbital fluctuations is also developed by applying the self-consistent renormalization theory of itinerant electron magnetism to orbital fluctuations. The critical end point, first-order transition, and crossover are described within Gaussian approximations of orbital fluctuations. We discuss the relevance of our results to CeAl 2 , CeCu 2 Si 2 , CeCu 2 Ge 2 , and related compounds, which all have low-lying crystalline-electric-field excited states. (author)

Molecular structure determination of cyclootane by ab initio and electron diffraction methods in the gas phase

OpenAIRE

De Almeida, Wagner B.

2000-01-01

The determination of the molecular structure of molecules is of fundamental importance in chemistry. X-rays and electron diffraction methods constitute in important tools for the elucidation of the molecular structure of systems in the solid state and gas phase, respectively. The use of quantum mechanical molecular orbital ab initio methods offer an alternative for conformational analysis studies. Comparison between theoretical results and those obtained experimentally in the gas phase can ma...

GridOrbit public display

DEFF Research Database (Denmark)

Ramos, Juan David Hincapie; Tabard, Aurélien; Bardram, Jakob

2010-01-01

We introduce GridOrbit, a public awareness display that visualizes the activity of a community grid used in a biology laboratory. This community grid executes bioin-formatics algorithms and relies on users to donate CPU cycles to the grid. The goal of GridOrbit is to create a shared awareness about...

[1012.5676] The Exoplanet Orbit Database

Science.gov (United States)

: The Exoplanet Orbit Database Authors: Jason T Wright, Onsi Fakhouri, Geoffrey W. Marcy, Eunkyu Han present a database of well determined orbital parameters of exoplanets. This database comprises parameters, and the method used for the planets discovery. This Exoplanet Orbit Database includes all planets

Fast Electron Repulsion Integrals for Molecular Coulomb Sturmians

DEFF Research Database (Denmark)

Avery, James Emil

2013-01-01

A new method is presented for calculating interelectron repulsion integrals for molecular Coulomb Sturmian basis sets. This makes use of an expansion of densities in terms of 2k-Sturmians, and the interelectron repulsion integrals are then calculated by a method based on the theory of hyperspheri......A new method is presented for calculating interelectron repulsion integrals for molecular Coulomb Sturmian basis sets. This makes use of an expansion of densities in terms of 2k-Sturmians, and the interelectron repulsion integrals are then calculated by a method based on the theory...... of hyperspherical harmonics. A rudimentary software library has been implemented and preliminary benchmarks indicate very good performance: On average 40 ns, or approximately 80 clock cycles, per electron repulsion integral. This makes molecular Coulomb Sturmians competitive with Gaussian type orbitals in terms...

Studies on molecular structure, vibrational spectra and molecular docking analysis of 3-Methyl-1,4-dioxo-1,4-dihydronaphthalen-2-yl 4-aminobenzoate

Science.gov (United States)

Suresh, D. M.; Amalanathan, M.; Hubert Joe, I.; Bena Jothy, V.; Diao, Yun-Peng

2014-09-01

The molecular structure, vibrational analysis and molecular docking analysis of the 3-Methyl-1,4-dioxo-1,4-dihydronaphthalen-2-yl 4-aminobenzoate (MDDNAB) molecule have been carried out using FT-IR and FT-Raman spectroscopic techniques and DFT method. The equilibrium geometry, harmonic vibrational wave numbers, various bonding features have been computed using density functional method. The calculated molecular geometry has been compared with experimental data. The detailed interpretation of the vibrational spectra has been carried out by using VEDA program. The hyper-conjugative interactions and charge delocalization have been analyzed using natural bond orbital (NBO) analysis. The simulated FT-IR and FT-Raman spectra satisfactorily coincide with the experimental spectra. The PES and charge analysis have been made. The molecular docking was done to identify the binding energy and the Hydrogen bonding with the cancer protein molecule.

An Overview of the Jupiter Europa Orbiter Concept's Europa Science Phase Orbit Design

Science.gov (United States)

Lock, Robert E.; Ludwinski, Jan M.; Petropoulos, Anastassios E.; Clark, Karla B.; Pappalardo, Robert T.

2009-01-01

Jupiter Europa Orbiter (JEO), the proposed NASA element of the proposed joint NASA-ESA Europa Jupiter System Mission (EJSM), could launch in February 2020 and conceivably arrive at Jupiter in December of 2025. The concept is to perform a multi-year study of Europa and the Jupiter system, including 30 months of Jupiter system science and a comprehensive Europa orbit phase of 9 months. This paper provides an overview of the JEO concept and describes the Europa Science phase orbit design and the related science priorities, model pay-load and operations scenarios needed to conduct the Europa Science phase. This overview is for planning and discussion purposes only.

Methods of orbit correction system optimization

International Nuclear Information System (INIS)

Chao, Yu-Chiu.

1997-01-01

Extracting optimal performance out of an orbit correction system is an important component of accelerator design and evaluation. The question of effectiveness vs. economy, however, is not always easily tractable. This is especially true in cases where betatron function magnitude and phase advance do not have smooth or periodic dependencies on the physical distance. In this report a program is presented using linear algebraic techniques to address this problem. A systematic recipe is given, supported with quantitative criteria, for arriving at an orbit correction system design with the optimal balance between performance and economy. The orbit referred to in this context can be generalized to include angle, path length, orbit effects on the optical transfer matrix, and simultaneous effects on multiple pass orbits

Discrete symmetries in periodic-orbit theory

International Nuclear Information System (INIS)

Robbins, J.M.

1989-01-01

The application of periodic-orbit theory to systems which possess a discrete symmetry is considered. A semiclassical expression for the symmetry-projected Green's function is obtained; it involves a sum over classical periodic orbits on a symmetry-reduced phase space, weighted by characters of the symmetry group. These periodic orbits correspond to trajectories on the full phase space which are not necessarily periodic, but whose end points are related by symmetry. If the symmetry-projected Green's functions are summed, the contributions of the unperiodic orbits cancel, and one recovers the usual periodic-orbit sum for the full Green's function. Several examples are considered, including the stadium billiard, a particle in a periodic potential, the Sinai billiard, the quartic oscillator, and the rotational spectrum of SF 6

Orbital welding technique

International Nuclear Information System (INIS)

Hoeschen, W.

2003-01-01

The TIG (Tungsten-inert gas) orbital welding technique is applied in all areas of pipe welding. The process is mainly used for austenitic and ferritic materials but also for materials like aluminium, nickel, and titanium alloys are commonly welded according to this technique. Thin-walled as well as thick-walled pipes are welded economically. The application of orbital welding is of particular interest in the area of maintenance of thick-walled pipes that is described in this article. (orig.) [de

Application of Semi-analytical Satellite Theory orbit propagator to orbit determination for space object catalog maintenance

Science.gov (United States)

Setty, Srinivas J.; Cefola, Paul J.; Montenbruck, Oliver; Fiedler, Hauke

2016-05-01

Catalog maintenance for Space Situational Awareness (SSA) demands an accurate and computationally lean orbit propagation and orbit determination technique to cope with the ever increasing number of observed space objects. As an alternative to established numerical and analytical methods, we investigate the accuracy and computational load of the Draper Semi-analytical Satellite Theory (DSST). The standalone version of the DSST was enhanced with additional perturbation models to improve its recovery of short periodic motion. The accuracy of DSST is, for the first time, compared to a numerical propagator with fidelity force models for a comprehensive grid of low, medium, and high altitude orbits with varying eccentricity and different inclinations. Furthermore, the run-time of both propagators is compared as a function of propagation arc, output step size and gravity field order to assess its performance for a full range of relevant use cases. For use in orbit determination, a robust performance of DSST is demonstrated even in the case of sparse observations, which is most sensitive to mismodeled short periodic perturbations. Overall, DSST is shown to exhibit adequate accuracy at favorable computational speed for the full set of orbits that need to be considered in space surveillance. Along with the inherent benefits of a semi-analytical orbit representation, DSST provides an attractive alternative to the more common numerical orbit propagation techniques.

(e,2e) momentum spectroscopic study of the C=C π orbitals of the vinyl halides

International Nuclear Information System (INIS)

Gorunganthu, R.R.; Coplan, M.A.; Leung, K.T.; Tossell, J.A.; Moore, J.H.; Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1, Canada; Department of Chemistry, University of Maryland, College Park, Maryland 20742)

1989-01-01

The distribution of electron momentum density has been measured for the outermost occupied orbitals of the vinyl halides and ethylene using the (e,2e) technique. In contrast to the ionization potentials for these π orbitals which decrease monotonically from vinyl fluoride to vinyl iodide, the values of the momenta where the distributions are a maximum, p max , increase from the fluoride through the bromide and then shift back to a lower value for the iodide. This observation can be analyzed in terms of B(r), the Fourier transform of the observed momentum distribution, and ΔB(r), the difference between B(r) functions. The shape of ΔB(r) for the fluoride, chloride, and bromide in comparison to ethylene reflects the effect of the carbon--halogen antibonding interaction in these vinyl halides. On the other hand, in vinyl iodide the antibonding interaction is compensated for by the diffuse iodine 5p character of the molecular orbital. The relation of these observations to chemical properties of the vinyl halides is discussed along with differences between experiment and calculations at low momentum

Large orbit neoclassical transport

International Nuclear Information System (INIS)

Lin, Z.; Tang, W.M.; Lee, W.W.

1997-01-01

Neoclassical transport in the presence of large ion orbits is investigated. The study is motivated by the recent experimental results that ion thermal transport levels in enhanced confinement tokamak plasmas fall below the open-quotes irreducible minimum levelclose quotes predicted by standard neoclassical theory. This apparent contradiction is resolved in the present analysis by relaxing the basic neoclassical assumption that the ions orbital excursions are much smaller than the local toroidal minor radius and the equilibrium scale lengths of the system. Analytical and simulation results are in agreement with trends from experiments. The development of a general formalism for neoclassical transport theory with finite orbit width is also discussed. copyright 1997 American Institute of Physics

Pyrene Molecular Orbital Shuffle-Controlling Excited State and Redox Properties by Changing the Nature of the Frontier Orbitals.

Science.gov (United States)

Merz, Julia; Fink, Julian; Friedrich, Alexandra; Krummenacher, Ivo; Al Mamari, Hamad H; Lorenzen, Sabine; Haehnel, Martin; Eichhorn, Antonius; Moos, Michael; Holzapfel, Marco; Braunschweig, Holger; Lambert, Christoph; Steffen, Andreas; Ji, Lei; Marder, Todd B

2017-09-21

We show that by judicious choice of substituents at the 2- and 7-positions of pyrene, the frontier orbital order of pyrene can be modified, giving enhanced control over the nature and properties of the photoexcited states and the redox potentials. Specifically, we introduced a julolidine-like moiety and Bmes 2 (mes=2,4,6-Me 3 C 6 H 2 ) as very strong donor (D) and acceptor (A), respectively, giving 2,7-D-π-D- and unsymmetric 2,7-D-π-A-pyrene derivatives, in which the donor destabilizes the HOMO-1 and the acceptor stabilizes the LUMO+1 of the pyrene core. Consequently, for 2,7-substituted pyrene derivatives, unusual properties are obtained. For example, very large bathochromic shifts were observed for all of our compounds, and unprecedented green light emission occurs for the D/D system. In addition, very high radiative rate constants in solution and in the solid state were recorded for the D-π-D- and D-π-A-substituted compounds. All compounds show reversible one-electron oxidations, and Jul 2 Pyr exhibits a second oxidation, with the largest potential splitting (ΔE=440 mV) thus far reported for 2,7-substituted pyrenes. Spectroelectrochemical measurements confirm an unexpectedly strong coupling between the 2,7-substituents in our pyrene derivatives. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Closed orbit related problems: Correction, feedback, and analysis

International Nuclear Information System (INIS)

Bozoki, E.S.

1995-01-01

Orbit correction - moving the orbit to a desired orbit, orbit stability - keeping the orbit on the desired orbit using feedback to filter out unwanted noise, and orbit analysis - to learn more about the model of the machine, are strongly interrelated. They are the three facets of the same problem. The better one knows the model of the machine, the better the predictions that can be made on the behavior of the machine (inverse modeling) and the more accurately one can control the machine. On the other hand, one of the tools to learn more about the machine (modeling) is to study and analyze the orbit response to open-quotes kicks.close quotes

Self-interaction corrected density functional calculations of molecular Rydberg states

International Nuclear Information System (INIS)

Gudmundsdóttir, Hildur; Zhang, Yao; Weber, Peter M.; Jónsson, Hannes

2013-01-01

A method is presented for calculating the wave function and energy of Rydberg excited states of molecules. A good estimate of the Rydberg state orbital is obtained using ground state density functional theory including Perdew-Zunger self-interaction correction and an optimized effective potential. The total energy of the excited molecule is obtained using the Delta Self-Consistent Field method where an electron is removed from the highest occupied orbital and placed in the Rydberg orbital. Results are presented for the first few Rydberg states of NH 3 , H 2 O, H 2 CO, C 2 H 4 , and N(CH 3 ) 3 . The mean absolute error in the energy of the 33 molecular Rydberg states presented here is 0.18 eV. The orbitals are represented on a real space grid, avoiding the dependence on diffuse atomic basis sets. As in standard density functional theory calculations, the computational effort scales as NM 2 where N is the number of orbitals and M is the number of grid points included in the calculation. Due to the slow scaling of the computational effort with system size and the high level of parallelism in the real space grid approach, the method presented here makes it possible to estimate Rydberg electron binding energy in large molecules

Combining molecular docking and QSAR studies for modeling the anti-tyrosinase activity of aromatic heterocycle thiosemicarbazone analogues

Science.gov (United States)

Dong, Huanhuan; Liu, Jing; Liu, Xiaoru; Yu, Yanying; Cao, Shuwen

2018-01-01

A collection of thirty-six aromatic heterocycle thiosemicarbazone analogues presented a broad span of anti-tyrosinase activities were designed and obtained. A robust and reliable two-dimensional quantitative structure-activity relationship model, as evidenced by the high q2 and r2 values (0.848 and 0.893, respectively), was gained based on the analogues to predict the quantitative chemical-biological relationship and the new modifier direction. Inhibitory activities of the compounds were found to greatly depend on molecular shape and orbital energy. Substituents brought out large ovality and high highest-occupied molecular orbital energy values helped to improve the activity of these analogues. The molecular docking results provided visual evidence for QSAR analysis and inhibition mechanism. Based on these, two novel tyrosinase inhibitors O04 and O05 with predicted IC50 of 0.5384 and 0.8752 nM were designed and suggested for further research.

Multi-reference approach to the calculation of photoelectron spectra including spin-orbit coupling

Energy Technology Data Exchange (ETDEWEB)

Grell, Gilbert; Bokarev, Sergey I., E-mail: sergey.bokarev@uni-rostock.de; Kühn, Oliver [Institut für Physik, Universität Rostock, D-18051 Rostock (Germany); Winter, Bernd; Seidel, Robert [Helmholtz-Zentrum Berlin für Materialien und Energie, Methods for Material Development, Albert-Einstein-Strasse 15, D-12489 Berlin (Germany); Aziz, Emad F. [Helmholtz-Zentrum Berlin für Materialien und Energie, Methods for Material Development, Albert-Einstein-Strasse 15, D-12489 Berlin (Germany); Department of Physics, Freie Universität Berlin, Arnimalle 14, D-14159 Berlin (Germany); Aziz, Saadullah G. [Chemistry Department, Faculty of Science, King Abdulaziz University, 21589 Jeddah (Saudi Arabia)

2015-08-21

X-ray photoelectron spectra provide a wealth of information on the electronic structure. The extraction of molecular details requires adequate theoretical methods, which in case of transition metal complexes has to account for effects due to the multi-configurational and spin-mixed nature of the many-electron wave function. Here, the restricted active space self-consistent field method including spin-orbit coupling is used to cope with this challenge and to calculate valence- and core-level photoelectron spectra. The intensities are estimated within the frameworks of the Dyson orbital formalism and the sudden approximation. Thereby, we utilize an efficient computational algorithm that is based on a biorthonormal basis transformation. The approach is applied to the valence photoionization of the gas phase water molecule and to the core ionization spectrum of the [Fe(H{sub 2}O){sub 6}]{sup 2+} complex. The results show good agreement with the experimental data obtained in this work, whereas the sudden approximation demonstrates distinct deviations from experiments.

Real-time orbit feedback at the APS

International Nuclear Information System (INIS)

Carwardine, J.

1998-01-01

A real-time orbit feedback system has been implemented at the Advanced Photon Source in order to meet the stringent orbit stability requirements. The system reduces global orbit motion below 30Hz by a factor of four to below 5 microm rms horizontally and 2 microm rms vertically. This paper focuses on dynamic orbit stability and describes the all-digital orbit feedback system that has been implemented at the APS. Implementation of the global orbit feedback system is described and its latest performance is presented. Ultimately, the system will provide local feedback at each x-ray source point using installed photon BPMs to measure x-ray beam position and angle directly. Technical challenges associated with local feedback and with dynamics of the associated corrector magnets are described. The unique diagnostic capabilities provided by the APS system are discussed with reference to their use in identifying sources of the underlying orbit motion

Dopamine and Caffeine Encapsulation within Boron Nitride (14,0) Nanotubes: Classical Molecular Dynamics and First Principles Calculations.

Science.gov (United States)

García-Toral, Dolores; González-Melchor, Minerva; Rivas-Silva, Juan F; Meneses-Juárez, Efraín; Cano-Ordaz, José; H Cocoletzi, Gregorio

2018-06-07

Classical molecular dynamics (MD) and density functional theory (DFT) calculations are developed to investigate the dopamine and caffeine encapsulation within boron nitride (BN) nanotubes (NT) with (14,0) chirality. Classical MD studies are done at canonical and isobaric-isothermal conditions at 298 K and 1 bar in explicit water. Results reveal that both molecules are attracted by the nanotube; however, only dopamine is able to enter the nanotube, whereas caffeine moves in its vicinity, suggesting that both species can be transported: the first by encapsulation and the second by drag. Findings are analyzed using the dielectric behavior, pair correlation functions, diffusion of the species, and energy contributions. The DFT calculations are performed according to the BLYP approach and applying the atomic base of the divided valence 6-31g(d) orbitals. The geometry optimization uses the minimum-energy criterion, accounting for the total charge neutrality and multiplicity of 1. Adsorption energies in the dopamine encapsulation indicate physisorption, which induces the highly occupied molecular orbital-lower unoccupied molecular orbital gap reduction yielding a semiconductor behavior. The charge redistribution polarizes the BNNT/dopamine and BNNT/caffeine structures. The work function decrease and the chemical potential values suggest the proper transport properties in these systems, which may allow their use in nanobiomedicine.

Interrater reliability of sonographic examinations of orbital fractures

International Nuclear Information System (INIS)

Siegfried, Jank; Martina, Deibl; Heinrich, Strobl; Andreas, Oberrauch; Alessandro, Nicasi; Martin, Missmann; Gerd, Bodner

2005-01-01

Objective: The purpose of this study is to determine whether there are statistically significant variations among different observers when examining fractures of the orbital walls. Material and methods: From December 2003 to April 2004, 28 patients with clinically suspected orbital fractures were examined by ultrasound prospectively. The US images of the infra-orbital margins, the orbital floors, the medial and lateral orbital walls of each patient were reexamined by two independent investigators. Results: Computed tomography revealed fractures of the orbital floor in 28 out of 31 patients (90.3%). The infra-orbital margins showed fractures of 14 of 31 patients (45.2%). The ultrasound examinations of the orbits by the three examiners presented satisfactory correlation regarding sensitivity and specificity. There were no significant differences between investigators. There was good agreement among the ultrasound examiners regarding the infra-orbital margins. This was not the case for the orbital floors. Conclusions: If there are clear cut clinical findings ultrasound examination could represent an alternative to computed tomography. If the clinical findings were indeterminate, computed tomography was essential as implicated by this study. Accordingly, further evaluation of ultrasound examinations of fractures of the orbital margins and floors are necessary

Molecular features related to HIV integrase inhibition obtained from structure- and ligand-based approaches.

Directory of Open Access Journals (Sweden)

Luciana L de Carvalho

Full Text Available Among several biological targets to treat AIDS, HIV integrase is a promising enzyme that can be employed to develop new anti-HIV agents. The aim of this work is to propose a mechanistic interpretation of HIV-1 integrase inhibition and to rationalize the molecular features related to the binding affinity of studied ligands. A set of 79 HIV-1 integrase inhibitors and its relationship with biological activity are investigated employing 2D and 3D QSAR models, docking analysis and DFT studies. Analyses of docking poses and frontier molecular orbitals revealed important features on the main ligand-receptor interactions. 2D and 3D models presenting good internal consistency, predictive power and stability were obtained in all cases. Significant correlation coefficients (r(2 = 0.908 and q(2= 0.643 for 2D model; r(2= 0.904 and q(2= 0.719 for 3D model were obtained, indicating the potential of these models for untested compounds. The generated holograms and contribution maps revealed important molecular requirements to HIV-1 IN inhibition and several evidences for molecular modifications. The final models along with information resulting from molecular orbitals, 2D contribution and 3D contour maps should be useful in the design of new inhibitors with increased potency and selectivity within the chemical diversity of the data.

Evolution of the Orbital Elements for Geosynchronous Orbit of Communications Satellite, II

Directory of Open Access Journals (Sweden)

Kyu-Hong Choi

1987-06-01

Full Text Available For a geostationary satellite north-south station keeping maneuver must control the inclination elements. The effects on the orbit plane of maneuvers and natural perturbations may be represented by a plane plot of Wc versus Ws, since these inclination elements represent the projection of the unit orbit normal onto the equatorial plane. The evolution of the semi-major axis and the inclination elements are obtained.

The international environment UNISPACE '82 and the ITU: A relationship between orbit-spectrum resource allocation and orbital debris

Science.gov (United States)

Olmstead, D.

1985-01-01

The 1985 Space WARC will examine and potentially modify the current geostationary orbit spectrum resource allocation methodology. Discussions in this international political environment could likely associate the geostationary orbital debris issue with the politicized issue of orbit spectrum allocation.

Advances in the management of orbital fractures.

Science.gov (United States)

Nguyen, P N; Sullivan, P

1992-01-01

Great progress has been made in both the basic science and the clinical knowledge base used in orbital reconstruction. With this, increasing complex orbital reconstructive problems are better managed. The diagnosis, treatment plan, and the actual reconstruction have evolved to a higher level. Several areas of progress are of note: the greater appreciation of the intimate relation between the bony orbit's shape and the position of the globe; application of computer technology in orbital injuries; effect of rigid fixation on autogenous and alloplastic graft; and the use of advanced biocompatible synthetic materials in orbital reconstruction. Although this progress has great impact on treatment of orbital injuries, there are many unanswered challenges in the treatment of the fragile frame of the window to the human soul.

Scanning probe methods applied to molecular electronics

Energy Technology Data Exchange (ETDEWEB)

Pavlicek, Niko

2013-08-01

Scanning probe methods on insulating films offer a rich toolbox to study electronic, structural and spin properties of individual molecules. This work discusses three issues in the field of molecular and organic electronics. An STM head to be operated in high magnetic fields has been designed and built up. The STM head is very compact and rigid relying on a robust coarse approach mechanism. This will facilitate investigations of the spin properties of individual molecules in the future. Combined STM/AFM studies revealed a reversible molecular switch based on two stable configurations of DBTH molecules on ultrathin NaCl films. AFM experiments visualize the molecular structure in both states. Our experiments allowed to unambiguously determine the pathway of the switch. Finally, tunneling into and out of the frontier molecular orbitals of pentacene molecules has been investigated on different insulating films. These experiments show that the local symmetry of initial and final electron wave function are decisive for the ratio between elastic and vibration-assisted tunneling. The results can be generalized to electron transport in organic materials.

Real-time orbit feedback at the APS

International Nuclear Information System (INIS)

Carwardine, J.A.; Lenkszus, F.R.

1998-01-01

A real-time orbit feedback system has been implemented at the Advanced Photon Source in order to meet the stringent orbit stability requirements. The system reduces global orbit motion below 30 Hz by a factor of four to below 5 μm rms horizontally and 2 μm rms vertically. This paper focuses on dynamic orbit stability and describes the all-digital orbit feedback system that has been implemented at the APS. Implementation of the global orbit feedback system is described and its latest performance is presented. Ultimately, the system will provide local feedback at each x-ray source point using installed photon BPMs to measure x-ray beam position and angle directly. Technical challenges associated with local feedback and with dynamics of the associated corrector magnets are described. The unique diagnostic capabilities provided by the APS system are discussed with reference to their use in identifying sources of the underlying orbit motion. copyright 1998 American Institute of Physics

Real-time orbit feedback at the APS.

Energy Technology Data Exchange (ETDEWEB)

Carwardine, J.

1998-06-18

A real-time orbit feedback system has been implemented at the Advanced Photon Source in order to meet the stringent orbit stability requirements. The system reduces global orbit motion below 30Hz by a factor of four to below 5{micro}m rms horizontally and 2{micro}m rms vertically. This paper focuses on dynamic orbit stability and describes the all-digital orbit feedback system that has been implemented at the APS. Implementation of the global orbit feedback system is described and its latest performance is presented. Ultimately, the system will provide local feedback at each x-ray source point using installed photon BPMs to measure x-ray beam position and angle directly. Technical challenges associated with local feedback and with dynamics of the associated corrector magnets are described. The unique diagnostic capabilities provided by the APS system are discussed with reference to their use in identifying sources of the underlying orbit motion.

Theory of orbital magnetoelectric response

International Nuclear Information System (INIS)

Malashevich, Andrei; Souza, Ivo; Coh, Sinisa; Vanderbilt, David

2010-01-01

We extend the recently developed theory of bulk orbital magnetization to finite electric fields, and use it to calculate the orbital magnetoelectric (ME) response of periodic insulators. Working in the independent-particle framework, we find that the finite-field orbital magnetization can be written as a sum of three gauge-invariant contributions, one of which has no counterpart at zero field. The extra contribution is collinear with and explicitly dependent on the electric field. The expression for the orbital magnetization is suitable for first-principles implementations, allowing one to calculate the ME response coefficients by numerical differentiation. Alternatively, perturbation-theory techniques may be used, and for that purpose we derive an expression directly for the linear ME tensor by taking the first field-derivative analytically. Two types of terms are obtained. One, the 'Chern-Simons' term, depends only on the unperturbed occupied orbitals and is purely isotropic. The other, 'Kubo' terms, involve the first-order change in the orbitals and give isotropic as well as anisotropic contributions to the response. In ordinary ME insulators all terms are generally present, while in strong Z 2 topological insulators only the Chern-Simons term is allowed, and is quantized. In order to validate the theory, we have calculated under periodic boundary conditions the linear ME susceptibility for a 3D tight-binding model of an ordinary ME insulator, using both the finite-field and perturbation-theory expressions. The results are in excellent agreement with calculations on bounded samples.

Electron-nuclear dynamics of molecular systems

International Nuclear Information System (INIS)

Diz, A.; Oehrn, Y.

1994-01-01

The content of an ab initio time-dependent theory of quantum molecular dynamics of electrons and atomic nuclei is presented. Employing the time-dependent variational principle and a family of approximate state vectors yields a set of dynamical equations approximating the time-dependent Schroedinger equation. These equations govern the time evolution of the relevant state vector parameters as molecular orbital coefficients, nuclear positions, and momenta. This approach does not impose the Born-Oppenheimer approximation, does not use potential energy surfaces, and takes into account electron-nuclear coupling. Basic conservation laws are fully obeyed. The simplest model of the theory employs a single determinantal state for the electrons and classical nuclei and is implemented in the computer code ENDyne. Results from this ab-initio theory are reported for ion-atom and ion-molecule collisions

Small Orbital Stereo Tracking Camera Technology Development

Science.gov (United States)

Gagliano, L.; Bryan, T.; MacLeod, T.

On-Orbit Small Debris Tracking and Characterization is a technical gap in the current National Space Situational Awareness necessary to safeguard orbital assets and crew. This poses a major risk of MOD damage to ISS and Exploration vehicles. In 2015 this technology was added to NASAs Office of Chief Technologist roadmap. For missions flying in or assembled in or staging from LEO, the physical threat to vehicle and crew is needed in order to properly design the proper level of MOD impact shielding and proper mission design restrictions. Need to verify debris flux and size population versus ground RADAR tracking. Use of ISS for In-Situ Orbital Debris Tracking development provides attitude, power, data and orbital access without a dedicated spacecraft or restricted operations on-board a host vehicle as a secondary payload. Sensor Applicable to in-situ measuring orbital debris in flux and population in other orbits or on other vehicles. Could enhance safety on and around ISS. Some technologies extensible to monitoring of extraterrestrial debris as well To help accomplish this, new technologies must be developed quickly. The Small Orbital Stereo Tracking Camera is one such up and coming technology. It consists of flying a pair of intensified megapixel telephoto cameras to evaluate Orbital Debris (OD) monitoring in proximity of International Space Station. It will demonstrate on-orbit optical tracking (in situ) of various sized objects versus ground RADAR tracking and small OD models. The cameras are based on Flight Proven Advanced Video Guidance Sensor pixel to spot algorithms (Orbital Express) and military targeting cameras. And by using twin cameras we can provide Stereo images for ranging & mission redundancy. When pointed into the orbital velocity vector (RAM), objects approaching or near the stereo camera set can be differentiated from the stars moving upward in background.

Orbital debris: a technical assessment

National Research Council Canada - National Science Library

Committee on Space Debris, National Research Council

..., and other debris created as a byproduct of space operations. Orbital Debris examines the methods we can use to characterize orbital debris, estimates the magnitude of the debris population, and assesses the hazard that this population poses to spacecraft...

Progress in reconstruction of orbital wall after fracture

Directory of Open Access Journals (Sweden)

Lu-Lu Xu

2018-04-01

Full Text Available At present, the orbital wall fracture is a very common facial trauma. The orbital contents are often incarcerated in the fracture cracks resulting in changes in the orbital eye position, then can bring a lifetime of diplopia and enophthalmos, which greatly affects the visual acuity and facial appearance. The purpose of repairing of orbital fracture is reconstructing orbital wall, repairing defect to correct eye position, avoiding enophthalmos and recovering visual function. The review will provide a comprehensive overview of orbital fracture reconstruction.

Effects of styrene unit on molecular conformation and spectral properties of CNsbnd PhCHdbnd NPhCHdbnd CHPhsbnd CN

Science.gov (United States)

Fang, Zhengjun; Wu, Feng; Jiao, Yingchun; Wang, Nanfang; Au, Chaktong; Cao, Chenzhong; Yi, Bing

2018-05-01

Compound CN-PhCH=NPhCH=CHPh-CN with both stilbene and benzylidene aniline units was synthesized, and studied from the viewpoint of molecular conformation and spectroscopic property by a combined use of experimental and computational methods. The maximum UV absorption wavelength (λmax) of the compound in ethanol, acetonitrile, chloroform and cyclohexane solvents were measured, and the 13C NMR chemical shift value δC(Cdbnd N) in chloroform-d was determined. The crystal structure of the compound was determined by X-ray diffraction. The frontier molecular orbital was calculated by density functional theory method. The results show that the UV absorption spectrum of the titled compound is similar to those of Schiff bases, while there is a larger red shift of λmax comparing to that of CN-PhCH=NPh-CN. Moreover, the molecular configuration of the titled compound relative to Cdbnd N is anti-form, having a more obvious twisted structure. The spectral and structural behaviors are further supported by the results of frontier molecular orbital analyses, NBO, electrostatic potentials and TD-DFT calculations. The study provides deeper insights into the molecular conformation of Schiff bases.

Optimal selection of Orbital Replacement Unit on-orbit spares - A Space Station system availability model

Science.gov (United States)

Schwaab, Douglas G.

1991-01-01

A mathematical programing model is presented to optimize the selection of Orbital Replacement Unit on-orbit spares for the Space Station. The model maximizes system availability under the constraints of logistics resupply-cargo weight and volume allocations.

The acute orbit: Differentiation of orbital cellulitis from subperiosteal abscess by computerized tomography

International Nuclear Information System (INIS)

Handler, L.C.; Davey, I.C.; Hill, J.C.; Lauryssen, C.

1991-01-01

A series of 65 patients suffering from acute inflammatory disease of the orbit was studied by CT. Ethmoiditis was the cause in the vast majority; trauma and dental extraction played a lesser role in causation. Orbital cellulitis was diagnosed in 17 and subperiosteal abscess in the remaining 48. It was not possible to differentiate 33 pus-containing abscesses from the six with inflammatory masses (phlegmons). The satisfactory response to aggressive medical treatment in those patients with inflammatory masses that were not drained justifies a more conservative approach; surgical drainage being reserved for those with a deterioration in proptosis, ocular movements or vision. Six abscesses arose de novo, of which some were in the orbital fat rather than the subperiosteal space. (orig.)

An Ontological Architecture for Orbital Debris Data

OpenAIRE

Rovetto, Robert J.

2017-01-01

The orbital debris problem presents an opportunity for inter-agency and international cooperation toward the mutually beneficial goals of debris prevention, mitigation, remediation, and improved space situational awareness (SSA). Achieving these goals requires sharing orbital debris and other SSA data. Toward this, I present an ontological architecture for the orbital debris domain, taking steps in the creation of an orbital debris ontology (ODO). The purpose of this ontological system is to ...

Study of orbit stability in the SSRF storage ring

International Nuclear Information System (INIS)

Dai Zhimin; Liu Guimin; Huang Nan

2003-01-01

In this paper, analysis of the beam orbit stability and conceptual study of the dynamic orbit feedback in the SSRF storage ring are presented. It is shown that beam orbit position movement at the photon source points is smaller than the orbit stability requirements in horizontal plane, but exceeds the orbit stability requirements in vertical plane. A dynamic global orbit feedback system, which consists of 38 high-bandwidth air-coil correctors and 40 high-precise BPMs, is proposed to suppress the vertical beam orbit position movement. Numerical simulations show that this dynamic orbit feedback system can stabilize the vertical beam orbit position movement in the frequency range up to 100 Hz

Stability of orbits around planetary satellites considering a disturbing body in an elliptical orbit: Applications to Europa and Ganymede

Science.gov (United States)

Cardoso dos Santos, Josué; Carvalho, Jean Paulo; Vilhena de Moraes, Rodolpho

Europa and Ganymede are two of the four Jupiter’s moons which compose the Galilean satellite. These ones are planetary satellites of greater interest at the present moment among the scientific community. There are some missions being planned to visit them and and the Jovian system. One of them is the cooperation between NASA and ESA for the Europa Jupiter System Mission (EJSM). In this mission are planned the insertion of the spacecrafts JEO (Jupiter Europa Orbiter) and JGO (Jupiter Ganymede Orbiter) into Europa and Ganymede’s orbit. Thus, there is a great necessity for having a better comprehension of the dynamics of the orbits around this planetary satellite. This comprehension is essential for the success of this type of mission. In this context, this work aims to perform a search for low-altitude orbits around these planetary satellites. An emphasis is given in polar orbits. These orbits can be useful in the planning of aerospace activities to be conducted around this planetary satellite, with respect to the stability of orbits of artificial satellites. The study considers orbits of an artificial satellite around Europa and Ganymede under the influence of the third-body perturbation (the gravitational attraction of Jupiter) and the polygenic perturbations. These last ones occur due to forces such as the non-uniform distribution of mass (J2 and J3) of the main (central) body. A simplified dynamic model for polygenic perturbations is used. A new model for the third-body disturbance is presented considering it in an elliptical orbit. The Lagrange planetary equations, which compose a system of nonlinear differential equations, are used to describe the orbital motion of the artificial satellite around Ganymede. The equations showed here are developed in closed form to avoid expansions in inclination and eccentricity.