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The vertical ionization potentials of N2, F2 and H2O were calculated by perturbation corrections to Koopmans' theorem using six different basis sets. The largest set used includes several sets of polarization functions. Comparison is made with measured values and with results of computations using Green's functions.
Radial distribution function change due to small long-range interaction imposition on short range potential
Ordinary Rayleigh-Schroudinger perturbation theory with Moller-Plesset (RSMP) partitioning is used to calculate second- and third-order correlation corrections to the CHF polarizability and dipole moment of the water molecule by a finite-field procedure. Pade approximants are found to be useful in accelerating the convergence of the property perturbation expansions. Field-induced polarization functions suitable for polarizability calculations are determined. The average polarizability calculated, neglecting vibrational averaging, with Dunning's (9s5p/4s-4s2p/2s) contracted GTO basis set augmented by field-induced lslp2d/lp polarization functions is within 3 per cent of the experimental result. Correlation corrections to the dipole moment and polarizability of the water molecule calculated by the finite-field RSMP and single + double excitation CI(SDCI) methods for the same basis set are found to be in close agreement. The RSMP approach has the advantages of being size-consistent and of being capable of greater efficiency than the SCDI method. Comparative calculations carried out using Epstein-Nesbet partitioning show that through third order RSEN correlation perturbation expansions for the dipole moment and polarizability are less rapidly convergent than RSMP expansions. However, reasonable accord with RSMP results can be achieved by using Pade approximants to accelerate the convergence of RSEN energy perturbation expansions. The convergence of RSMP property correlation expansions based on the zeroth-order uncoupled-Hartree-Fock (UCHF) and coupled-Hartree-Fock (CHF) approximations are compared through third order. Whereas the CHF + RSMP expansions are for practical purposes fully converged, the UCHF + RSMP expansions are not adequately converged.
A perturbative correction to the method of configuration interaction with single substitutions (CIS) is presented. This CIS(D) correction approximately introduces the effect of double substitutions which are absent in CIS excited states. CIS(D) is a second-order perturbation expansion of the coupled-cluster excited state method, restricted to single and double substitutions, in a series in which CIS is zeroth order, and the first-order correction vanishes. CIS (D) excitation energies are size consistent and the calculational complexity scales with the fifth power of molecular size, akin to second-order Moller-Plesset theory for the ground state. Calculations on singlet excited states of ethylene, formaldehyde, acetaldehyde, butadiene and benzene show that CIS (D) is a uniform improvement over CIS. CIS(D) appears to be a promising method for examining excited states of large molecules, where more accurate methods are not feasible.
Azirinyl cation is an aromatic cyclic molecule that is isoelectronic with cyclopropenylidene, c-C3H2, and c-C3H3+. Cyclopropenylidene has been shown to be ubiquitous, existing in many different astrophysical environments. Given the similar chemistry between C and N, and the relative abundances between C and N in astrophysical environments, it is expected that there should be aromatic ringed molecules that incorporate N in the ring, but as yet, no such molecule has been identified. To address this issue, the present study uses high levels of electronic structure theory to compute a highly accurate quartic force field (QFF) for azirinyl cation and its two lowest lying isomers, the cyanomethyl and isocyanomethyl cations. The theoretical approach uses the singles and doubles coupled-cluster method that includes a perturbative correction for connected triple excitations, CCSD(T), together with extrapolation to the one-particle basis set limit and corrections for scalar relativity and core-correlation. The QFF is then used in a second order vibrational perturbation theory analysis (VPT2) to compute the fundamental vibrational frequencies and rovibrational spectroscopic constants for all three C2NH2+ isomers. The reliability of the VPT2 vibrational frequencies is tested by comparison to vibrational configuration interaction (VCI) calculations and excellent agreement is found between the two approaches. Fundamental vibrational frequencies and rovibrational spectroscopic constants for all singly substituted 13C, 15N, and D isotopologues are also reported. It is expected that the highly accurate spectroscopic data reported herein will be useful in the identification of these cations in high resolution experimental or astronomical observations.
A Kalman-Schmidt filter is used to estimate atmospheric and trajectory parameters for entry into the Venusian atmosphere. A significantly improved version of the Landing Trajectory Reconstruction (LTR) computer program, used to obtain the estimates is described. Major improvements involve precision and linearity control of numerical differencing, corrected perturbation modeling, and incorporation of a refractivity model. Important results show that gyroscopic data are not usable with LTR, that atmospheric properties are generally well estimated for altitudes less than 100 km, and that the two LTR modes of operation are complementary in performance.
Several new uses of satellite tethers are discussed, including: (1) using tether extension to reposition a satellite in orbit without fuel expenditure by extending a mass on the end of a tether; (2) using a tether for energy storage to power the satellite during eclipse; and (3) using a tether for eccentricity pumping to correct perturbations in the orbit and as a means of adding energy to the orbit for boosting and orbital transfer.
Several new uses of satellite tethers are discussed, including: (1) using tether extension to reposition a satellite in orbit without fuel expenditure by extending a mass on the end of a tether; (2) using a tether for energy storage to power the satellite during eclipse; and (3) using a tether for eccentricity pumping to correct perturbations in the orbit and as a means of adding energy to the orbit for boosting and orbital transfer.
The Rapid Advancement Preview Tracking (RAPT) control method uses both a nonlinear system model and a linearized system model to provide a form of feedback/preview control for nonlinear systems. It uses measurements of the states to calculate the current preview control signal from a local linearization of the state equations, and then iteratively calculates a perturbation correction for that control using the nonlinear equations. The corrected control signal is then applied to the system, driving the end-effector to the next position along a specified trajectory. Computer simulations of tracking control for two-link planar manipulators indicate that this algorithm may be fast enough for real-time control.
To meet the challenge of future deep space programs, an accurate and efficient engineering code for analyzing the shielding requirements against high-energy galactic heavy radiation is needed. To address this need, a new Green's function code capable of simulating high charge and energy ions with either laboratory or space boundary conditions is currently under development. The computational model consists of combinations of physical perturbation expansions based on the scales of atomic interaction, multiple scattering, and nuclear reactive processes with use of the Neumann-asymptotic expansions with non-perturbative corrections. The code contains energy loss due to straggling, nuclear attenuation, nuclear fragmentation with energy dispersion and downshifts. Previous reports show that the new code accurately models the transport of ion beams through a single slab of material. Current research efforts are focused on enabling the code to handle multiple layers of material and the present paper reports on progress made towards that end.
The transpiration method was used to determine the volatility of titanium dioxide (TiO2) in water vapor-containing environments at temperatures between 1473 and 1673 K. Water contents ranged from 0 to 76 mole % in oxygen or argon carrier gases for 20 to 250 hr exposure times. Results indicate that oxygen is not a key contributor to volatilization and the primary reaction for volatilization in this temperature range is: TiO2(s) + H2O(g) = TiO(OH)2(g). Data were analyzed with both the second and third law methods to extract an enthalpy and entropy of formation. The geometry and vibrational frequencies of TiO(OH)2(g) were computed using B3LYP density functional theory, and the enthalpy of formation was computed using the coupled-cluster singles and doubles method with a perturbative correction for connected triple substitutions [CCSD(T)]. Thermal functions are calculated using both a structure with bent and linear hydroxyl groups. Calculated second and third heats show closer agreement with the linear hydroxyl group, suggesting more experimental and computational spectroscopic and structural work is needed on this system.
A new class of linear multistep methods for numerical integration of differential equations is reported that permits satellite computation solutions to be corrected at certain points in the past as the integration advances in time. Algorithms have been developed for the solution of both first- and second-order differential equations. The back correction method appears to be more efficient than classical methods when dominant and perturbing forces can be separated.
Very high resolution two-dimensional simulations are used to test the generation and growth of the so-called 'minimal' k exp 4 power spectrum which develops from initial conditions which have power only on small scales, such as might result from some process in the early universe. It is confirmed that the amplitude of minimal long-wave power grows proportionally to a exp 4, not a-squared, where a is the scale factor of the expanding universe. It reverts to a-squared only after the short-wave modes are effectively saturated, and by that time an effective long-wave power law closer to k-cubed is found. Small-scale perturbations may result in much more long-wave power than has been generally assumed.
A method for geometric correction data calculation is based on decomposition of image distortions into nominal distortions and perturbations, caused by deviations from the nominal spacecraft motion and sensor pointing. The maximal errors of the method are of the order of 5 m, and the average errors are less than 0.6 m (sigma).
The ways an Independent Landing Monitor (ILM) may be used to complement the automatic landing function were studied. In particular, a systematic procedure was devised to establish the information and display requirements of an ILM during the landing phase of the flight. Functionally, the ILM system is designed to aid the crew in assessing whether the total system (e.g., avionics, aircraft, ground navigation aids, external disturbances) performance is acceptable, and, in case of anomaly, to provide adequate information to the crew to select the least unsafe of the available alternatives. Economically, this concept raises the possibility of reducing the primary autoland system redundancy and associated equipment and maintenance costs. The required level of safety for the overall system would in these cases be maintained by upgrading the backup manual system capability via the ILM. A safety budget analysis was used to establish the reliability requirements for the ILM. These requirements were used as constraints in devising the fault detection scheme. Covariance propagation methods were used with a linearized system model to establish the time required to correct manually perturbed states due to the fault. Time-to-detect and time-to-correct requirements were combined to devise appropriate altitudes and strategies for fault recovery.
A general formulation of the perturbation problem is studied, and a new approach, perturbation sequence expansion, is introduced for handling shock disturbances. The method is applied to unsteady effects, three-dimensional corrections to axisymmetric and two-dimensional flows, and wind tunnel corrections. The perturbation equations are nonlinear and can be solved by shock capturing methods.
Experiments have been conducted on materials in a single mode microwave resonator to test predictions of a new theory of microwave absorption by a lossy dielectric sphere. An analysis of cavity perturbation for verifying the new absorption model revealed a limitation of a standard form of cavity perturbation theory and led to a modification which generalized its application. The cavity perturbations of a nylon sphere were used to calculate the complex permittivity using the standard perturbation theory and the modified form. These permittivity values were compared to that determined from cavity perturbation using a thin nylon rod where the standard and modified forms agree. The results show that the modification is necessary to correctly apply perturbation theory to spherical samples. A second experiment confirmed the theoretical prediction that under certain sample conditions the power absorbed by a sphere in a resonant cavity can be maximum at a location in the cavity where the empty cavity electric field intensity is a minimum.
Computational formulas for first-order perturbation energy correction for singly excited singlet and triplet states of helium isoelectronic sequence