Coupled multiconfigurational self-consistent-field method of atomic dipole polarizabilities. I - Theory and application to carbon.
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Billingsley, F. P., II↗
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A self-consistent field method for galactic dynamics
The present study describes an algorithm for evolving collisionless stellar systems in order to investigate the evolution of systems with density profiles like the R exp 1/4 law, using only a few terms in the expansions. A good fit is obtained for a truncated isothermal distribution, which renders the method appropriate for galaxies with flat rotation curves. Calculations employing N of about 10 exp 6-7 are straightforward on existing supercomputers, making possible simulations having significantly smoother fields than with direct methods such as tree-codes. Orbits are found in a given static or time-dependent gravitational field; the potential, phi(r, t) is revised from the resultant density, rho(r, t). Possible scientific uses of this technique are discussed, including tidal perturbations of dwarf galaxies, the adiabatic growth of central masses in spheroidal galaxies, instabilities in realistic galaxy models, and secular processes in galactic evolution.
Hernquist, Lars↗
High Performance Parallel Computational Nanotechnology
At a recent press conference, NASA Administrator Dan Goldin encouraged NASA Ames Research Center to take a lead role in promoting research and development of advanced, high-performance computer technology, including nanotechnology. Manufacturers of leading-edge microprocessors currently perform large-scale simulations in the design and verification of semiconductor devices and microprocessors. Recently, the need for this intensive simulation and modeling analysis has greatly increased, due in part to the ever-increasing complexity of these devices, as well as the lessons of experiences such as the Pentium fiasco. Simulation, modeling, testing, and validation will be even more important for designing molecular computers because of the complex specification of millions of atoms, thousands of assembly steps, as well as the simulation and modeling needed to ensure reliable, robust and efficient fabrication of the molecular devices. The software for this capacity does not exist today, but it can be extrapolated from the software currently used in molecular modeling for other applications: semi-empirical methods, ab initio methods, self-consistent field methods, Hartree-Fock methods, molecular mechanics; and simulation methods for diamondoid structures. In as much as it seems clear that the application of such methods in nanotechnology will require powerful, highly powerful systems, this talk will discuss techniques and issues for performing these types of computations on parallel systems. We will describe system design issues (memory, I/O, mass storage, operating system requirements, special user interface issues, interconnects, bandwidths, and programming languages) involved in parallel methods for scalable classical, semiclassical, quantum, molecular mechanics, and continuum models; molecular nanotechnology computer-aided designs (NanoCAD) techniques; visualization using virtual reality techniques of structural models and assembly sequences; software required to control mini robotic manipulators for positional control; scalable numerical algorithms for reliability, verifications and testability. There appears no fundamental obstacle to simulating molecular compilers and molecular computers on high performance parallel computers, just as the Boeing 777 was simulated on a computer before manufacturing it.
Saini, Subhash↗
Level shifts and inelastic electron scattering in dense plasmas
A completely quantum mechanical formalism has been developed to describe the high density plasma effects on fundamental atomic parameters. Both the bound and free electrons are treated by a method which in principle is similar to Hartree's self-consistent field method. The free plasma electrons' wavefunction is obtained from the Schroedinger equation with the effective potential representing the spherically averaged Coulomb interaction with bound and free electrons. Results are given for level shifts, coefficients of transition probabilities, and electron collision cross sections of Ne(9+) for temperatures of 200 and 500 eV for an electron density range of 1-6 x 10 to the 24th per cu cm.
Davis, J.↗
Systems of self-gravitating particles in general relativity and the concept of an equation of state
Equilibrium configurations of self-gravitating particles systems by self consistent fields method
Bonazzola, S.↗
N(+)-N long-range interaction energies and resonance charge exchange
The aerothermodynamic studies of proposed space missions require atmospheric charge-transfer data. N2(+) eigenstate energies are calculated with use of the complete-active-space self-consistent-field method with an extended Gaussian basis set. The N(+)-N charge-exchange cross section, determined from these energies, agrees with merged-beam measurements. This contradicts the previous theoretical conclusion. A simple physical description of the long-range interaction is presented and should expedite future charge-transfer studies.
Stallcop, J. R.↗
Theoretical calculation of ozone vibrational infrared intensities
An ab initio dipole moment function for ozone has been computed using the CASSCF (complete active space self-consistent field) method, and forms the basis for a calculation of ozone infrared band intensities. Vibrational wave functions were generated using the variational method with potential energy surfaces derived from experimental force constants. Computed values of the permanent dipole moment, dipole moment derivatives, and infrared band strengths are all found to be in remarkably good agreement with experiment. Intensities are predicted for hot bands for which experimental values are unavailable, and implications for atmospheric ozone spectroscopy are discussed. As the dipole moment matrix element signs are now established for nearly all of the observed bands, further refinement of the dipole moment function is possible.
Adler-Golden, S. M.↗
Linear and nonlinear dynamic instability of rotating polytropes
A three-dimensional hydrodynamic computer program is used to study the growth of nonaxisymmetric structures in rapidly rotating, self-gravitating polytropes. Models with polytropic index n = 0.8, 1.0, 1.3, 1.5, and 1.8 are studied. The initially axisymmetric equilibria are constructed by the Ostriker-Mark self-consistent-field method. The nonaxisymmetric pattern that develops out of low-amplitude random noise is a two-armed spiral with a well-defined pattern speed and growth rate which closely match properties of the toroidal mode predicted from the linear, second-order tensor-virial equation. A Fourier analysis of each polytrope's azimuthal density distribution shows that, even in the linear amplitude regime, higher-order angular patterns also develop exponentially in time. The higher-order patterns ultimately move in synchronization with the broad two-armed spiral, creating a narrow two-armed spiral. As the polytropic index is decreased, a more open and centrally more barlike pattern develops.
Williams, Harold A.↗
Ab initio atomic recombination reaction energetics on model heat shield surfaces
Ab initio quantum mechanical calculations on small hydration complexes involving the nitrate anion are reported. The self-consistent field method with accurate basis sets has been applied to compute completely optimized equilibrium geometries, vibrational frequencies, thermochemical parameters, and stable site labilities of complexes involving 1, 2, and 3 waters. The most stable geometries in the first hydration shell involve in-plane waters bridging pairs of nitrate oxygens with two equal and bent hydrogen bonds. A second extremely labile local minimum involves out-of-plane waters with a single hydrogen bond and lies about 2 kcal/mol higher. The potential in the region of the second minimum is extremely flat and qualitatively sensitive to changes in the basis set; it does not correspond to a true equilibrium structure.
Senese, Fredrick↗
Numerical results in the statistical theory of thermal turbulence
Several statistical theories of turbulence are applied to thermal convection problem, and are compared in a series of numerical calculations. Results are presented for both the case of very large and very small Prandtl numbers, and for moderate Rayleigh numbers. The theories compared are the direct-interaction approximation, the self-consistent field approximation, the quasi-linear approximation, the quasi-normal approximation, and a 'Markovianized' quasi-normal approximation. Results for these theories are then compared with some simple exact solutions to the statistical problem. The results indicate that the direct-interaction and the self-consistent field method give satisfactory results at all Rayleigh numbers investigated, whereas the procedures based on the quasi-normal approximation give sensible results only at small Rayleigh numbers.
Herring, J. R.↗
The Transition from Hydrogen Bonding to Ionization in (HCI)n(NH3)n and (HCI)n(H2O)n Clusters: Consequences for Anharmonic Vibrational Spectroscopy
Anharmonic vibrational frequencies and intensities are calculated for 1:1 and 2:2 (HCl)(sub n)(NH3)(sub n) and (HCl)(sub n)(H2O)(sub n) complexes, employing the correlation-corrected vibrational self-consistent field method with ab initio potential surfaces at the MP2/TZP computational level. In this method, the anharmonic coupling between all vibrational modes is included, which is found to be important for the systems studied. For the 4:4 (HCl)(sub n)(H2O)(sub n) complex, the vibrational spectra are calculated at the harmonic level, and anharmonic effects are estimated. Just as the (HCl)(sub n)(NH3)(sub n) structure switches from hydrogen-bonded to ionic for n=2, the (HCl)(sub n)(H2O)(sub n) switches to ionic structure for n=4. For (HCl)2(H2O)2, the lowest energy structure corresponds to the hydrogen-bonded form. However, configurations of the ionic form are separated from this minimum by a barrier of less than an O-H stretching quantum. This suggests the possibility of experiments on ionization dynamics using infrared excitation of the hydrogen-bonded form. The strong cooperative effects on the hydrogen bonding, and concomitant transition to ionic bonding, makes an accurate estimate of the large anharmonicity crucial for understanding the infrared spectra of these systems. The anharmonicity is typically of the order of several hundred wave numbers for the proton stretching motions involved in hydrogen or ionic bonding, and can also be quite large for the intramolecular modes. In addition, the large cooperative effects in the 2:2 and higher order (HCl(sub n)(H2O)(sub n) complexes may have interesting implications for solvation of hydrogen halides at ice surfaces.
Chaban, Galina M.↗
Ab initio calculations of anharmonic vibrational spectroscopy for hydrogen fluoride (HF)n (n = 3, 4) and mixed hydrogen fluoride/water (HF)n(H2O)n (n = 1, 2, 4) clusters
Anharmonic vibrational frequencies and intensities are computed for hydrogen fluoride clusters (HF)n, with n = 3, 4 and mixed clusters of hydrogen fluoride with water (HF)n(H2O)n where n = 1, 2. For the (HF)4(H2O)4 complex, the vibrational spectra are calculated at the harmonic level, and anharmonic effects are estimated. Potential energy surfaces for these systems are obtained at the MP2/TZP level of electronic structure theory. Vibrational states are calculated from the potential surface points using the correlation-corrected vibrational self-consistent field method. The method accounts for the anharmonicities and couplings between all vibrational modes and provides fairly accurate anharmonic vibrational spectra that can be directly compared with experimental results without a need for empirical scaling. For (HF)n, good agreement is found with experimental data. This agreement shows that the Moller-Plesset (MP2) potential surfaces for these systems are reasonably reliable. The accuracy is best for the stiff intramolecular modes, which indicates the validity of MP2 in describing coupling between intramolecular and intermolecular degrees of freedom. For (HF)n(H2O)n experimental results are unavailable. The computed intramolecular frequencies show a strong dependence on cluster size. Intensity features are predicted for future experiments.
Water/chemistry↗
Cluster calculation of carbon monoxide on a Cu surface using the self-consistent-field-X-alpha-scattered-wave method
Two geometries of CO chemisorbed on a Cu(100) surface have been studied using the self-consistent-field-X-alpha-scattered-wave method. Both geometries assume the CO molecule is bonded to the Cu surface with the C end down; one geometry is in the fourfold-symmetric hole site and one is directly on top of a Cu atom. The calculated valence density of states for the fourfold-symmetry case gives a satisfactory interpretation of the two main peaks below the copper d band in the UV photoemission spectra (UPS). A third weaker peak of the UPS data can be correlated with a CO molecule adsorbed directly on top of a copper atom.
Yu, H. L.↗
Method of the self-consistent field in general relativity and its application to the gravitational geon.
Free-space einstein equations for concentrations of radiation held together by gravitational attraction, investigating gravity wave perturbations on background metric
GRAVITATIONAL FIELD↗
Integral processing in beyond-Hartree-Fock calculations
The increasing rate at which improvements in processing capacity outstrip improvements in input/output performance of large computers has led to recent attempts to bypass generation of a disk-based integral file. The direct self-consistent field (SCF) method of Almlof and co-workers represents a very successful implementation of this approach. This paper is concerned with the extension of this general approach to configuration interaction (CI) and multiconfiguration-self-consistent field (MCSCF) calculations. After a discussion of the particular types of molecular orbital (MO) integrals for which -- at least for most current generation machines -- disk-based storage seems unavoidable, it is shown how all the necessary integrals can be obtained as matrix elements of Coulomb and exchange operators that can be calculated using a direct approach. Computational implementations of such a scheme are discussed.
Taylor, P. R.↗
The use of projection in SCF spin density calculations.
Spin-projected unrestricted self-consistent field /SCF/ methods for spin density calculations used to determine hyperfine coupling constants
SPIN-ORBIT INTERACTION↗
Calculations of molecular ionization energies using a self-consistent-charge Hartree-Fock-Slater method
A numerical-variational method for performing self-consistent molecular calculations in the Hartree-Fock-Slater (HFS) model is presented. Molecular wavefunctions are expanded in terms of basis sets constructed from numerical HFS solutions of selected one-center atomlike problems. Binding energies and wavefunctions for the molecules are generated using a discrete variational method for a given molecular potential. In the self-consistent-charge (SCC) approximation to the complete self-consistent-field (SCF) method, results of a Mulliken population analysis of the molecular eigenfunctions are used in each iteration to produce 'atomic' occupation numbers. The simplest SCC potential is then obtained from overlapping spherical atomlike charge distributions. Molecular ionization energies are calculated using the transition-state procedure; results are given for CO, H2O, H2S, AlCl, InCl, and the Ni5O surface complex. Agreement between experimental and theoretical ionization energies for the free-molecule valence levels is generally within 1 eV. The simple SCC procedure gives a reasonably good approximation to the molecular potential, as shown by comparison with experiment, and with complete SCF calculations for CO, H2O, and H2S.
Rosen, A.↗
The protonation of N2O reexamined - A case study on the reliability of various electron correlation methods for minima and transition states
The protonation of N2O and the intramolecular proton transfer in N2OH(+) are studied using various basis sets and a variety of methods, including second-order many-body perturbation theory (MP2), singles and doubles coupled cluster (CCSD), the augmented coupled cluster (CCSD/T/), and complete active space self-consistent field (CASSCF) methods. For geometries, MP2 leads to serious errors even for HNNO(+); for the transition state, only CCSD/T/ produces a reliable geometry due to serious nondynamical correlation effects. The proton affinity at 298.15 K is estimated at 137.6 kcal/mol, in close agreement with recent experimental determinations of 137.3 +/- 1 kcal/mol.
Martin, J. M. L.↗