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At least 307 records · Page 17
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

A Generalized Variational Principle with Applications to Excited State Mean Field Theory

We present a generalization of the variational principle that is compatible with any Hamiltonian eigenstate that can be specified uniquely by a list of properties. This variational principle appears to be compatible with a wide range of electronic structure methods, including mean field theory, density functional theory, multireference theory, and quantum Monte Carlo. Like the standard variational principle, this generalized variational principle amounts to the optimization of a nonlinear function that, in the limit of an arbitrarily flexible wave function, has the desired Hamiltonian eigenstate as its global minimum. Unlike the standard variational principle, it can target excited states and select individual states in cases of degeneracy or near-degeneracy. As an initial demonstration of how this approach can be useful in practice, we employ it to improve the optimization efficiency of excited state mean field theory by an order of magnitude. With this improved optimization, we are able to demonstrate that the accuracy of the corresponding second-order perturbation theory rivals that of singles-and-doubles equation-of-motion coupled cluster in a substantially broader set of molecules than could be explored by our previous optimization methodology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Photo response of 164 Dy

Background: Little data is available for the pygmy dipole resonance (PDR) in axially deformed nuclei. Photon-scattering experiments are complicated by high level densities in the PDR region and the small energy difference of transitions to the ground state and to excited states. Purpose: In this work, we report on an experimental study of the low-energy dipole strength distribution of the well-deformed nucleus 164 Dy between 4.0–7.7 MeV. Methods: The low-lying photoresponse of 164 Dy has been investigated using the method of nuclear resonance fluorescence using a quasimonochromatic linearly polarized $\textit{γ}$-ray beam in the energy range of 4.0–7.7 MeV in steps of 0.2 MeV. Results: For excitation energies between 4 MeV and 5 MeV, sufficiently low level densities allow for the identification of individual states, including level energies, reduced transition widths and branching ratios. Energy-averaged mean decay branching ratios, mean population ratios and partial absorption cross sections were determined above 5 MeV up to the neutron-separation threshold at 7.7 MeV. A Lorentzian-shaped enhancement of the partial photo absorption cross section followed by decays back to the ground-state band is found at 6.10(5) MeV with a width of 0.77(23) MeV. A comparison with results from complementary measurements is performed using the framework of the statistical model. Conclusions: The experimental results for the mean population ratios deviate systematically from the statistical model simulation by 30(6)%. However, they are in agreement within one standard deviation of the simulation.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2022

Computing x-ray absorption spectra from linear-response particles atop optimized holes

State specific orbital optimized density functional theory (OO-DFT) methods, such as restricted open-shell Kohn–Sham (ROKS), can attain semiquantitative accuracy for predicting x-ray absorption spectra of closed-shell molecules. OO-DFT methods, however, require that each state be individually optimized. In this Communication, we present an approach to generate an approximate core-excited state density for use with the ROKS energy ansatz, which is capable of giving reasonable accuracy without requiring state-specific optimization. Herein, this is achieved by fully optimizing the core-hole through the core-ionized state, followed by the use of electron-addition configuration interaction singles to obtain the particle level. This hybrid approach can be viewed as a DFT generalization of the static-exchange (STEX) method and can attain ~0.6 eV rms error for the K-edges of C–F through the use of local functionals, such as PBE and OLYP. This ROKS(STEX) approach can also be used to identify important transitions for full OO ROKS treatment and can thus help reduce the computational cost of obtaining OO-DFT quality spectra. ROKS(STEX), therefore, appears to be a useful technique for the efficient prediction of x-ray absorption spectra.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Relativistic coupled‐cluster and equation‐of‐motion coupled‐cluster methods

Abstract The development of relativistic coupled‐cluster (CC) and equation‐of‐motion coupled‐cluster (EOM‐CC) methods is reviewed. An emphasis is placed on recent efforts to improve the computational efficiency of CC and EOM‐CC calculations with non‐perturbative treatments of spin‐orbit coupling (SO‐CC and EOM‐CC) by partially recovering spin symmetry in the formulations. Example calculations of electronic ground state as well as valence‐excited and core‐excited states for molecules containing heavy elements are presented to demonstrate the applicability and usefulness of the SO‐CC and EOM‐CC methods. Future directions for the development of the SO‐CC and EOM‐CC methods are also discussed. This article is categorized under: Electronic Structure Theory > Ab Initio Electronic Structure Methods

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Algorithm advances and applications of time‐dependent first‐principles simulations for ultrafast dynamics

Abstract Far from equilibrium phenomenon is a central theme of contemporary material research. Such phenomenon can exhibit itself in atomic structure and dynamics, but very often it also happens as non‐equilibrium phenomenon in the electronic structure. In ab initio material simulation, density functional theory (DFT) has played an essential role in studying electronic ground state problems. For excited states, besides many‐body perturbation theory, another powerful tool is the time dependent DFT (TDDFT) method. In particular, the real‐time TDDFT (rt‐TDDFT) method can be used to simulate many non‐equilibrium phenomena directly. Here we introduce our works on some algorithm advances based on our recently rt‐TDDFT method. This method uses the plane‐wave basis set, and significantly accelerates its efficiency by increasing the time step from 0.1–1 as in traditional methods to 0.2–0.5 fs. The noncollinear magnetic moments and spin–orbit coupling have also been included in our rt‐TDDFT method. Furthermore, a Boltzmann‐TDDFT algorithm has been developed to solve the hot carrier overheating problem in Ehrenfest dynamics, and a natural orbital branching algorithm has been developed to overcome the mean‐field approximation in Ehrenfest dynamics nuclear trajectory, thus allows stochastic multiple paths in chemical reactions. Utilizing these methods, we have studied the photoinduced ultrafast demagnetization, ultrafast phase transition, energy transfer between plasmon and hot carriers, as well as the high‐energy ion implantation and low‐energy atomic diffusion in semiconductors. We believe the tools as the ones introduced here can enable us to study a wide range of phenomena which are of great interest in modern day material research. This article is categorized under: Structure and Mechanism > Computational Materials Science Electronic Structure Theory > Ab Initio Electronic Structure Methods Electronic Structure Theory > Density Functional Theory

Liu, Wen‐Hao↗
DOE OSTI2023

Lifetime measurements in 206 Po with a shell-model interpretation

The lifetimes of the first excited 2⁺ and 4⁺ states in 206 Po were measured using the recoil-distance Dopplershift method. The experimental results were compared to large-scale shell-model calculations that describe the deduced transition probabilities well. Those calculations were extended to the neighboring 204,208 Po isotopes giving a good overall description of the yrast states. However, the calculations underpredict the energies of the 6+1 and 8+1 states, which suggests that further improvement of the proton-neutron interaction is required.

190 ≤ A ≤ 219↗
DOE OSTI2021

Polymer thin films as universal substrates for extreme ultraviolet absorption spectroscopy of molecular transition metal complexes

Polystyrene and polyvinyl chloride thin films are explored as sample supports for extreme ultraviolet (XUV) spectroscopy of molecular transition metal complexes. Thin polymer films prepared by slip-coating are flat and smooth, and transmit much more XUV light than silicon nitride windows. Analytes can be directly cast onto the polymer surface or co-deposited within it. The M-edge XANES spectra (40–90 eV) of eight archetypal transition metal complexes (M = Mn, Fe, Co, Ni) are presented to demonstrate the versatility of this method. The films are suitable for pump/probe transient absorption spectroscopy, as shown by the excited-state spectra of Fe(bpy) 3 2+ in two different polymer supports.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2023

Neutral band gap of carbon by quantum Monte Carlo methods

We present a method of calculating the energy gap of a charge-neutral excitation using only ground-state calculations. We report Quantum Monte Carlo calculations of Γ→ Γ and Γ → X particle-hole excitation energies in diamond carbon. We analyze the finite-size effect and find the same 1/L decay rate as that in a charged excitation, where L is the linear extension of the supercell. This slow decay is attributed to the delocalized nature of the excitation in supercells too small to accommodate excitonic binding effects. At larger system sizes, the apparent 1/L decay crosses over to a 1/L 3 behavior. Estimation of the scale of exciton binding can be used to correct finite-size effects of neutral gaps.

36 MATERIALS SCIENCE↗
NASA NTRS1975

Douglas Experience in Flight Flutter Testing

Douglas Aircraft Company experience in flight flutter testing is reviewed briefly, with comments on state-of-the-art excitation and instrumentation techniques used up to the present time. The limitations of previous techniques are discussed with emphasis on the problem of: (1) establishing a flutter margin of safety for predicted marginal flutter modes; (2) resolving instances of flutter not predicted by theoretical calculations in advance; and (3) delaying the airplane demonstration by time consumed in acquisition and reduction of flutter data. Current Douglas philosophy in flight flutter testing is presented and a description given of steady-state vane excitation system development, automatic data handling system, and the potential application of automatic computing methods for increasing flutter data yield.

Philbrick, J.↗
NASA NTRS1989

A fully-coupled implicit method for thermo-chemical nonequilibrium air at sub-orbital flight speeds

A CFD technique is described in which the finite-rate chemistry in thermal and chemical nonequilibrium air is fully and implicitly coupled with the fluid motion. Developed for use in the suborbital hypersonic flight speed range, the method accounts for nonequilibrium vibrational and electronic excitation and dissociation, but not ionization. The steady-state solution to the resulting system of equations is obtained by using a lower-upper factorization and symmetric Gauss-Seidel sweeping technique through Newton iteration. Inversion of the left-hand-side matrices is replaced by scalar multiplications through the use of the diagonal dominance algorithm. The code, named CENS2H (Compressible-Euler-Navier-Stokes Two-Dimensional Hypersonic), is fully vectorized and requires about 8.8 x 10 to the -5th sec per node point per iteration using a Cray X-MP computer. Converged solutions are obtained after about 2400 iterations. Sample calculations are made for a circular cylinder and a 10 percent airfoil at 5 deg angle of attack. The calculated cylinder flow field agrees with that obtained experimentally. The code predicts a 10 percent change in lift, drag, and pitching moment for the airfoil due to the thermochemical phenomena.

Park, Chul↗
NASA NTRS1992

Numerical simulations of non-equilibrium shock layers with efficient implicit schemes

Current and future calculations of nonequilibrium shock layers require the use of a very large number of equations, due to a multiplicity of chemical species, excited states, and internal energy modes. The computational cost associated with the use of standard implicit methods becomes prohibitive; it is therefore desirable to examine the potential of several methods and determine if any can be projected to be more efficient and accurate for large systems of equations. Here, the performance of several implicit schemes on several simple practical examples of reacting flows is examined. The Euler equations are solved by three different implicit methods, and two methods of coupling between the fluid dynamics and the chemistry are studied. Several cases of stiffness are considered and both 1D and 2D examples are computed.

Cambier, Jean-Luc↗
NASA NTRS1994

Theoretical Study of the Low-Lying States of MgN+2

The structure and binding energies of the low-lying states of MgN2+ have been computed at the multireference configuration interaction level of theory. The effect of Mg inner-shell correlation have been included using the core-polarization potential method. The charge-quadrupole interaction results in a linear 2Sigma+ ground state as expected. The excited states can arise from either the interaction of the 2-P state of Mg+ with N2 or from charge transfer states with Mg(sup 2+)N2- bonding character. The lowest lying excited state, 2-B2, is mixture of these two mechanisms, which results in a C2v, geometry with Mg atoms sitting at the N2 bond midpoint. The small barrier in the bending potential exists between this state and the 2-II State which is the lowest lying linear excited state.

Maitre, Philippe↗
NASA NTRS2006

Adjoint-Based Algorithms for Adaptation and Design Optimizations on Unstructured Grids

Schemes based on discrete adjoint algorithms present several exciting opportunities for significantly advancing the current state of the art in computational fluid dynamics. Such methods provide an extremely efficient means for obtaining discretely consistent sensitivity information for hundreds of design variables, opening the door to rigorous, automated design optimization of complex aerospace configuration using the Navier-Stokes equation. Moreover, the discrete adjoint formulation provides a mathematically rigorous foundation for mesh adaptation and systematic reduction of spatial discretization error. Error estimates are also an inherent by-product of an adjoint-based approach, valuable information that is virtually non-existent in today's large-scale CFD simulations. An overview of the adjoint-based algorithm work at NASA Langley Research Center is presented, with examples demonstrating the potential impact on complex computational problems related to design optimization as well as mesh adaptation.

Nielsen, Eric J.↗
DOE OSTI2023

New Dimensions in the Theory of Excited States and X-ray Spectra (Final Report)

This Final Technical Report briefly summarizes the achievements during the lifetime of our DOE BES grant DE-FG02-97ER45623. The long-term goal of this project has been the development of quantitative theories of the interaction between radiation and matter, with a focus on x-ray spectroscopies. X-ray spectra have long been among the most important probes of atomic-scale structure and properties of matter, ranging from atoms and molecular systems to condensed matter and exotic states. These spectroscopies are widely used in investigations at the major DOE synchrotron x-ray facilities and related centers world-wide. In addition to fundamental theory, a major goal of our project has been the development of computational software that implements the theory for calculations of x-ray spectra of various materials throughout the periodic table. Due to the complex nature of x-ray spectra, quantitative theory is essential for its interpretation. The theory is challenging since it involves excited state electronic structure and many-body correlation effects that go beyond independent particle approximations like DFT or Hartree-Fock. Moreover, the experimental investigations typically involve a broad range of energy, time, and temperature scales, from the UV-Vis to hard x-ray energies of order 10 4 eV, and temperatures T from ambient up to the warm-dense-matter regime where the Fermi energy kBTF is of order a few eV, i.e., temperatures of order 105 Kelvin. This broad range of experimental conditions has fostered many novel theoretical approaches and computational techniques, many of which we have developed systematically over the duration of the grant. In contrast to the traditional wave-function approach of quantum theory and electronic structure methods, our theoretical approach is based on modern Green's function techniques. This approach is better suited for aperiodic structures, excited states, and broad spectral ranges, since it avoids the computational bottlenecks of sum-over-states approaches, as in the Fermi golden rule. This theoretical framework has been incorporated into efficient, user-friendly x-ray spectroscopy software which is now used routinely worldwide to simulate and analyze spectra. These theoretical tools provide an essential complement to synchrotron and next-generation light sources, which are used to investigate complex materials with ever increasing precision. Moreover, the synergism between theory, computation and experiment contributed by our research enhances scientific understanding and creates opportunities for innovations in materials and energy science and in many fields. As documented in this Report, this research grant has been remarkably successful in achieving these goals. In particular, this grant has supported the development of the x-ray spectroscopy software suite known as FEFF (named for an effective scattering amplitude f eff in the theory). The FEFF codes have become one of the premier tools for quantitative simulations of x-ray spectra as documented by many thousands of citations in the Web of Science and Google-Scholar.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Excited state electronic structure of dimethyl disulfide involved in photodissociation at ∼200 nm

Dimethyl disulfide (DMDS), one of the smallest organic molecules with an S–S bond, serves as a model system for understanding photofragmentation in polypeptides and proteins. Prior studies of DMDS photodissociation excited at ∼266 nm and ∼248 nm have elucidated the mechanisms of S–S and C–S bond cleavage, which involve the lowest excited electronic states S 1 and S 2 . Far less is known about the dissociation mechanisms and electronic structure of relevant excited states of DMDS excited at ∼200 nm. Herein we present calculations of the electronic structure and properties of electronic states S 1 –S 6 accessed when DMDS is excited at ∼200 nm. Our analysis includes a comparison of theoretical and experimental UV spectra, as well as theoretically predicted one-dimensional cuts through the singlet and triplet potential energy surfaces along the S–S and C–S bond dissociation coordinates. Finally, we present calculations of spin–orbit coupling constants at the Franck–Condon geometry to assess the likelihood of ultrafast intersystem crossing. We show that choosing an accurate yet computationally efficient electronic structure method for calculating the S 0 –S 6 potential energy surfaces along relevant dissociation coordinates is challenging due to excited states with doubly excited character and/or mixed Rydberg-valence character. Our findings demonstrate that the extended multi-state complete active space second-order perturbation theory (XMS-CASPT2) balances this computational efficiency and accuracy, as it captures both the Rydberg character of states in the Franck–Condon region and multiconfigurational character toward the bond-dissociation limits. In conclusion, we compare the performance of XMS-CASPT2 to a new variant of equation of motion coupled cluster theory with single, double, and perturbative triple corrections, EOM-CCSD(T)(a)*, finding that EOM-CCSD(T)(a)* significantly improves the treatment of doubly excited states compared to EOM-CCSD, but struggles to quantitatively capture asymptotic energies along bond dissociation coordinates for these states.

Rishi, Varun↗
NASA NTRS1987

Full CI studies of the collinear transition state for the reaction F + H2 yields HF + H

Full CI calculations on the collinear transition state for the reaction F + H2 yields HF + H are reported. The full CI results are compared with those obtained from single-reference and multireference CI calculations and from single-reference CPF calculations. In general, only those methods which attempt to account for the effects of higher excitations, such as CPF or CI plus the Davidson correction, yield a transition-state location and barrier height in good agreement with the full CI. In an extended basis, the effect of higher excitations is estimated to lower the barrier by as much as 1.5 kcal/mol; such an effect would essentially eliminate the present discrepancy between theory and experiment.

Bauschlicher, Charles W., Jr.↗
DOE OSTI2024

Core-excited states in 105 Cd

105 Cd was produced in the 96 Mo+ 12 C fusion/evaporation reaction, performed at NIPNE, Bucharest-Magurele, Romania. Various excited states of positive- and negative-parities were populated. Picosecond half-lives were measured by using the Differential Decay Curve Method (DDCM) method, allowing to control the side feeding of the states of interest. Further, new data were obtained for the half-lives of the 11/2 + , 15/2 - and 19/2 -105 Cd states. Reduced electric quadrupole transition strengths were calculated and compared to the neighboring odd-A and even-A cadmium nuclei. The particle-core weak coupling approach was used to interpret excited states of 105 Cd in the light of the new data.

74 ATOMIC AND MOLECULAR PHYSICS↗
NASA NTRS1997

Collision Strengths for Electron Collisional Excitation of S II

Electron collisional excitation strengths for inelastic transitions in S II are calculated using the R-matrix method in a 19-state (3s(sup 2)3p(sup 3)(sup 4)S(sup o), (sup 2)D(sup o), (sup 2)p(sup o), 3s3p(sup 4)(sup 4)P, (sup 2)D, (sup 2)S, 3S(sup 2)3p(sup 2)3d(sup 2)P, (sup 4)F, (sup 4)D, (sup 2)F, (sup 4)P, 3s(sup 2)3p(sup 2)4s(sup 4)P, (sup 2)P, 3s(sup 2)3p(sup 2)4p(sup 2)S(s o), (sup 4)D(sup o), (sup 4)P(sup o), (sup 2)D(sup o), (sup 4)S(sup o), (sup 2)P(sup o)) close-coupling approximation. These target states are represented by extensive configuration-interaction wave functions that give excitation energies and oscillator strengths that are usually in good agreement with the experimental values and the available accurate calculations. The present results for collision strengths are in very good agreement with the recent merged beams energy loss measurement of Liao et al. and agree reasonably well with the 18-state R-matrix calculation of Ramsbottom, Bell, & Stafford, but show significant differences from the 12-state R-matrix calculation of Cai & Pradhan.

Tayal, S. S.↗