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At least 1,171 records · Page 65
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DOE OSTI2014

The Golden-Thompson inequality: Historical aspects and random matrix applications

The Golden-Thompson inequality, Tr (e{sup A+B}) ⩽ Tr (e{sup A}e{sup B}) for A, B Hermitian matrices, appeared in independent works by Golden and Thompson published in 1965. Both of these were motivated by considerations in statistical mechanics. In recent years the Golden-Thompson inequality has found applications to random matrix theory. In this article, we detail some historical aspects relating to Thompson's work, giving in particular a hitherto unpublished proof due to Dyson, and correspondence with Pólya. We show too how the 2 × 2 case relates to hyperbolic geometry, and how the original inequality holds true with the trace operation replaced by any unitarily invariant norm. In relation to the random matrix applications, we review its use in the derivation of concentration type lemmas for sums of random matrices due to Ahlswede-Winter, and Oliveira, generalizing various classical results.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2014

Base norms and discrimination of generalized quantum channels

We introduce and study norms in the space of hermitian matrices, obtained from base norms in positively generated subspaces. These norms are closely related to discrimination of so-called generalized quantum channels, including quantum states, channels, and networks. We further introduce generalized quantum decision problems and show that the maximal average payoffs of decision procedures are again given by these norms. We also study optimality of decision procedures, in particular, we obtain a necessary and sufficient condition under which an optimal 1-tester for discrimination of quantum channels exists, such that the input state is maximally entangled.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2014

A finite difference Davidson procedure to sidestep full ab initio hessian calculation: Application to characterization of stationary points and transition state searches

The cost of calculating nuclear hessians, either analytically or by finite difference methods, during the course of quantum chemical analyses can be prohibitive for systems containing hundreds of atoms. In many applications, though, only a few eigenvalues and eigenvectors, and not the full hessian, are required. For instance, the lowest one or two eigenvalues of the full hessian are sufficient to characterize a stationary point as a minimum or a transition state (TS), respectively. We describe here a method that can eliminate the need for hessian calculations for both the characterization of stationary points as well as searches for saddle points. A finite differences implementation of the Davidson method that uses only first derivatives of the energy to calculate the lowest eigenvalues and eigenvectors of the hessian is discussed. This method can be implemented in conjunction with geometry optimization methods such as partitioned-rational function optimization (P-RFO) to characterize stationary points on the potential energy surface. With equal ease, it can be combined with interpolation methods that determine TS guess structures, such as the freezing string method, to generate approximate hessian matrices in lieu of full hessians as input to P-RFO for TS optimization. This approach is shown to achieve significant cost savings relative to exact hessian calculation when applied to both stationary point characterization as well as TS optimization. The basic reason is that the present approach scales one power of system size lower since the rate of convergence is approximately independent of the size of the system. Therefore, the finite-difference Davidson method is a viable alternative to full hessian calculation for stationary point characterization and TS search particularly when analytical hessians are not available or require substantial computational effort.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2014

Spectroscopy of Mn atoms isolated in solid {sup 4}He

We present an experimental study of the laser-induced luminescence spectra of Mn atoms in solid helium matrices. We observe transitions of the valence electron and of inner-shell electrons. We find that the Mn-He interaction perturbs the inner-shell transitions to a lesser extent than the valence-electron transitions. The observed lineshapes of the inner-shell transitions of Mn are similar to those of an inner-shell transition in Ba studied earlier. At the same time, they are more strongly perturbed than the corresponding transitions in Au and Cu under the same conditions. We suggest a qualitative explanation of these observations based on the atomic bubble model. Our results also suggest that the inner-shell transitions of Mn in solid He are more strongly perturbed than the same lines of Mn isolated in solid Ar or Kr matrices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

On the spin separation of algebraic two-component relativistic Hamiltonians: Molecular properties

The idea for separating the algebraic exact two-component (X2C) relativistic Hamiltonians into spin-free (sf) and spin-dependent terms [Z. Li, Y. Xiao, and W. Liu, J. Chem. Phys. 137, 154114 (2012)] is extended to both electric and magnetic molecular properties. Taking the spin-free terms (which are correct to infinite order in α ≈ 1/137) as zeroth order, the spin-dependent terms can be treated to any desired order via analytic derivative technique. This is further facilitated by unified Sylvester equations for the response of the decoupling and renormalization matrices to single or multiple perturbations. For practical purposes, explicit expressions of order α{sup 2} in spin are also given for electric and magnetic properties, as well as two-electron spin-orbit couplings. At this order, the response of the decoupling and renormalization matrices is not required, such that the expressions are very compact and completely parallel to those based on the Breit-Pauli (BP) Hamiltonian. However, the former employ sf-X2C wave functions, whereas the latter can only use nonrelativistic wave functions. As the sf-X2C terms can readily be interfaced with any nonrelativistic program, the implementation of the O(α{sup 2}) spin-orbit corrections to sf-X2C properties requires only marginal revisions of the routines for evaluating the BP type of corrections.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Oxidation-resistant, solution-processed plasmonic Ni nanochain-SiO{sub x} (x < 2) selective solar thermal absorbers

Metal oxidation at high temperatures has long been a challenge in cermet solar thermal absorbers, which impedes the development of atmospherically stable, high-temperature, high-performance concentrated solar power (CSP) systems. In this work, we demonstrate solution-processed Ni nanochain-SiO{sub x} (x < 2) and Ni nanochain-SiO{sub 2} selective solar thermal absorbers that exhibit a strong anti-oxidation behavior up to 600 °C in air. The thermal stability is far superior to previously reported Ni nanoparticle-Al{sub 2}O{sub 3} selective solar thermal absorbers, which readily oxidize at 450 °C. The SiO{sub x} (x < 2) and SiO{sub 2} matrices are derived from hydrogen silsesquioxane and tetraethyl orthosilicate precursors, respectively, which comprise Si-O cage-like structures and Si-O networks. Fourier transform infrared spectroscopy shows that the dissociation of Si-O cage-like structures and Si-O networks at high temperatures have enabled the formation of new bonds at the Ni/SiO{sub x} interface to passivate the surface of Ni nanoparticles and prevent oxidation. X-ray photoelectron spectroscopy and Raman spectroscopy demonstrate that the excess Si in the SiO{sub x} (x < 2) matrices reacts with Ni nanostructures to form silicides at the interfaces, which further improves the anti-oxidation properties. As a result, Ni-SiO{sub x} (x < 2) systems demonstrate better anti-oxidation performance than Ni-SiO{sub 2} systems. This oxidation-resistant Ni nanochain-SiO{sub x} (x < 2) cermet coating also exhibits excellent high-temperature optical performance, with a high solar absorptance of ∼90% and a low emittance ∼18% measured at 300 °C. These results open the door towards atmospheric stable, high temperature, high-performance solar selective absorber coatings processed by low-cost solution-chemical methods for future generations of CSP systems.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Stability conditions for exact-exchange Kohn-Sham methods and their relation to correlation energies from the adiabatic-connection fluctuation-dissipation theorem

The occurrence of instabilities, in particular singlet-triplet and singlet-singlet instabilities, in the exact-exchange (EXX) Kohn-Sham method is investigated. Hessian matrices of the EXX electronic energy with respect to the expansion coefficients of the EXX effective Kohn-Sham potential in an auxiliary basis set are derived. The eigenvalues of these Hessian matrices determine whether or not instabilities are present. Similar as in the corresponding Hartree-Fock case instabilities in the EXX method are related to symmetry breaking of the Hamiltonian operator for the EXX orbitals. In the EXX methods symmetry breaking can easily be visualized by displaying the local multiplicative exchange potential. Examples (N{sub 2}, O{sub 2}, and the polyyne C{sub 10}H{sub 2}) for instabilities and symmetry breaking are discussed. The relation of the stability conditions for EXX methods to approaches calculating the Kohn-Sham correlation energy via the adiabatic-connection fluctuation-dissipation (ACFD) theorem is discussed. The existence or nonexistence of singlet-singlet instabilities in an EXX calculation is shown to indicate whether or not the frequency-integration in the evaluation of the correlation energy is singular in the EXX-ACFD method. This method calculates the Kohn-Sham correlation energy through the ACFD theorem theorem employing besides the Coulomb kernel also the full frequency-dependent exchange kernel and yields highly accurate electronic energies. For the case of singular frequency-integrands in the EXX-ACFD method a regularization is suggested. Finally, we present examples of molecular systems for which the self-consistent field procedure of the EXX as well as the Hartree-Fock method can converge to more than one local minimum depending on the initial conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

The electronic structure of VO in its ground and electronically excited states: A combined matrix isolation and quantum chemical (MRCI) study

The electronic ground and excited states of the vanadium monoxide (VO) molecule were studied in detail. Electronic absorption spectra for the molecule isolated in Ne matrices complement the previous gas-phase spectra. A thorough quantum chemical (multi-reference configuration interaction) study essentially confirms the assignment and characterization of the electronic excitations observed for VO in the gas-phase and in Ne matrices and allows the clarification of open issues. It provides a complete overview over the electronically excited states up to about 3 eV of this archetypical compound.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Analytic nuclear forces and molecular properties from full configuration interaction quantum Monte Carlo

Unbiased stochastic sampling of the one- and two-body reduced density matrices is achieved in full configuration interaction quantum Monte Carlo with the introduction of a second, “replica” ensemble of walkers, whose population evolves in imaginary time independently from the first and which entails only modest additional computational overheads. The matrices obtained from this approach are shown to be representative of full configuration-interaction quality and hence provide a realistic opportunity to achieve high-quality results for a range of properties whose operators do not necessarily commute with the Hamiltonian. A density-matrix formulated quasi-variational energy estimator having been already proposed and investigated, the present work extends the scope of the theory to take in studies of analytic nuclear forces, molecular dipole moments, and polarisabilities, with extensive comparison to exact results where possible. These new results confirm the suitability of the sampling technique and, where sufficiently large basis sets are available, achieve close agreement with experimental values, expanding the scope of the method to new areas of investigation.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Fluorinated noble-gas cyanides FKrCN, FXeCN, and FXeNC

We report on three new noble-gas molecules, FKrCN, FXeCN, and FXeNC, prepared in low-temperature Kr and Xe matrices. These molecules are made by UV photolysis of FCN in the matrices and subsequent thermal annealing. The FCN precursor is produced by deposition of the matrix gas containing (FCN){sub 3} through a microwave discharge. The new noble-gas molecules are assigned with the help of quantum chemical calculations at the MP2(full) and CCSD(T) levels of theory. Similar Ar compounds (FArCN and FArNC) as well as FKrNC are not found in these experiments, which is in agreement with the calculated energetics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Determining the band alignment of TbAs:GaAs and TbAs:In 0.53 Ga 0.47 As

Here, we propose and systematically justify a band structure for TbAs nanoparticles in GaAs and In 0.53 Ga 0.47 As host matrices. Moreover, fluence-dependent optical-pump terahertz-probe measurements suggest the TbAs nanoparticles have a band gap and provide information on the carrier dynamics, which are determined by the band alignment. Spectrophotometry measurements provide the energy of optical transitions in the nanocomposite systems and reveal a large blue shift in the absorption energy when the host matrix is changed from In 0.53 Ga 0.47 As to GaAs. Finally, Hall data provides the approximate Fermi level in each system. From this data, we deduce that the TbAs:GaAs system forms a type I (straddling) heterojunction and the TbAs:In 0.53 Ga 0.47 As system forms a type II (staggered) heterojunction.

36 MATERIALS SCIENCE↗
DOE OSTI2015

A generalized force-modified potential energy surface for mechanochemical simulations

We describe the modifications that a spatially varying external load produces on a Born-Oppenheimer potential energy surface (PES) by calculating static quantities of interest. The effects of the external loads are exemplified using electronic structure calculations (at the HF/6-31G{sup ∗∗} level) of two different molecules: ethane and hexahydro-1,3,5-trinitro-s-triazine (RDX). The calculated transition states and Hessian matrices of stationary points show that spatially varying external loads shift the stationary points and modify the curvature of the PES, thereby affecting the harmonic transition rates by altering both the energy barrier as well as the prefactor. The harmonic spectra of both molecules are blueshifted with increasing compressive “pressure.” Some stationary points on the RDX-PES disappear under application of the external load, indicating the merging of an energy minimum with a saddle point.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Acoustic scattering of a cylindrical quasi-Gaussian beam with arbitrary incidence focused on a rigid elliptical cylinder

Using the partial-wave series expansion method in cylindrical coordinates, a formal analytical solution for the acoustical scattering of a 2D cylindrical quasi-Gaussian beam with an arbitrary angle of incidence θ{sub i}, focused on a rigid elliptical cylinder in a non-viscous fluid, is developed. The cylindrical focused beam expression is an exact solution of the Helmholtz equation. The scattering coefficients for the elliptical cylinder are determined by forcing the expression of the total (incident + scattered) field to satisfy the Neumann boundary condition for a rigid immovable surface, and performing the product of matrices involving an inversion procedure. Computations for the matrices elements require a single numerical integration procedure for each partial-wave mode. Numerical results are performed with particular emphasis on the focusing properties of the incident beam and its angle of incidence with respect to the major axis a of the ellipse as well as the aspect ratio a/b where b is the minor axis (assuming a > b). The method is validated and verified against previous results obtained via the T-matrix for plane waves. The present analysis is the first to consider an acoustical beam on an elliptic cylinder of variable cross-section as opposed to plane waves of infinite extent. Other 2D non-spherical and Chebyshev surfaces are mentioned that may be examined throughout this analytical formalism assuming a small deformation parameter ε.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

PET based nanocomposite films for microwave packaging applications

In recent years, changes in life standards have promoted the diffusion of Ready to Cook (RTC) and Ready to Eat (RTE) products for microwave ovens. However, the main limits in microwave (MW) ovens usage are often related to the proper choice of packaging materials suitable for such technology. In fact, packages for microwaveable RTC and RTE foods should ensure adequate preservation of the product before cooking/heating such as high barriers to gases and aromas and adequate control of water vapor transmission. In addition, microwaveable packaging material must be transparent to MW, thermally stable and resistant to the mechanical stress induced by the accumulation in the head space of volatile substances produced during the cooking. Polymeric materials are good candidates for microwaveable packaging thanks to their transparency to MW. In the last years a great interest is devoted to developing innovative solution based on the use of additives or systems that act as susceptors or heating enhancers for improving the characteristics of polymers in cooking/heating in MW ovens. The present work was focused on the production and characterization of nanocomposite copolyester based films suitable for microwaveable food packaging applications. The matrices selected consist in two PET copolymers modified with carbon black (ULTRA STD) and with titanium oxide (ULTRA NA). Nanocomposite co-extruded multilayer films were produced using different percentages (0%, 2% and 4%wt/wt) of Cloisite 20A (C20A). Films were analyzed for evaluating the effect of nanofiller on the morphology and barrier properties. Moreover, to verify the effectiveness of the designed systems in reducing the cooking times of meat products, MW heating tests were carried out on pork meat hamburgers in MW oven at varying supplied powers. The cooking tests have pointed out that the selected matrices are efficient in reducing cooking times and that even low concentration of C20A acts as heating enhancers of PET.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2015

Matrix-isolation and ab initio study of HKrCCCl and HXeCCCl

We report on two new noble-gas molecules, HKrCCCl and HXeCCCl, prepared in low-temperature Kr and Xe matrices. These molecules are made by UV photolysis of HCCCl in the matrices and subsequent thermal annealing. The HCCCl precursor is produced by microwave discharge of a mixture of a matrix gas with trichloroethylene (HClC=CCl{sub 2}). The assignments of the new noble-gas molecules are supported by deuteration experiments and quantum chemical calculations at the MP2(full) and CCSD(T) levels of theory with the def2-TZVPPD basis set. No evidence of ClXeCCH, which is computationally reliably stable, is found in the experiments. ClKrCCH as well as the Ar compounds HArCCCl and ClArCCH are not observed either, which is in agreement with the calculations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Communication: Towards ab initio self-energy embedding theory in quantum chemistry

The self-energy embedding theory (SEET), in which the active space self-energy is embedded in the self-energy obtained from a perturbative method treating the non-local correlation effects, was recently developed in our group. In SEET, the double counting problem does not appear and the accuracy can be improved either by increasing the perturbation order or by enlarging the active space. This method was first calibrated for the 2D Hubbard lattice showing promising results. In this paper, we report an extension of SEET to quantum chemical ab initio Hamiltonians for applications to molecular systems. The self-consistent second-order Green’s function method is used to describe the non-local correlations, while the full configuration interaction method is carried out to capture strong correlation within the active space. Using few proof-of-concept examples, we show that SEET yields results of comparable quality to n-electron valence state second-order perturbation theory with the same active space, and furthermore, the full active space can be split into smaller active spaces without further implementation. Moreover, SEET avoids intruder states and does not require any high-order reduced density matrices. These advantages show that SEET is a promising method to describe physical and chemical properties of challenging molecules requiring large active spaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Chemical speciation of U, Fe, and Pu in melt glass from nuclear weapons testing

Nuclear weapons testing generates large volumes of glassy materials that influence the transport of dispersed actinides in the environment and may carry information on the composition of the detonated device. We determine the oxidation state of U and Fe (which is known to buffer the oxidation state of actinide elements and to affect the redox state of groundwater) in samples of melt glass collected from three U.S. nuclear weapons tests. For selected samples, we also determine the coordination geometry of U and Fe, and we report the oxidation state of Pu from one melt glass sample. We find significant variations among the melt glass samples and, in particular, find a clear deviation in one sample from the expected buffering effect of Fe(II)/Fe(III) on the oxidation state of uranium. In the first direct measurement of Pu oxidation state in a nuclear test melt glass, we obtain a result consistent with existing literature that proposes Pu is primarily present as Pu(IV) in post-detonation material. In addition, our measurements imply that highly mobile U(VI) may be produced in significant quantities when melt glass is quenched rapidly following a nuclear detonation, though these products may remain immobile in the vitrified matrices. The observed differences in chemical state among the three samples show that redox conditions can vary dramatically across different nuclear test conditions. The local soil composition, associated device materials, and the rate of quenching are all likely to affect the final redox state of the glass. The resulting variations in glass chemistry are significant for understanding and interpreting debris chemistry and the later environmental mobility of dispersed material.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Distillation of secret-key from a class of compound memoryless quantum sources

We consider secret-key distillation from tripartite compound classical-quantum-quantum (cqq) sources with free forward public communication under strong security criterion. We design protocols which are universally reliable and secure in this scenario. These are shown to achieve asymptotically optimal rates as long as a certain regularity condition is fulfilled by the set of its generating density matrices. We derive a multi-letter formula which describes the optimal forward secret-key capacity for all compound cqq sources being regular in this sense. We also determine the forward secret-key distillation capacity for situations where the legitimate sending party has perfect knowledge of his/her marginal state deriving from the source statistics. In this case regularity conditions can be dropped. Our results show that the capacities with and without the mentioned kind of state knowledge are equal as long as the source is generated by a regular set of density matrices. We demonstrate that regularity of cqq sources is not only a technical but also an operational issue. For this reason, we give an example of a source which has zero secret-key distillation capacity without sender knowledge, while achieving positive rates is possible if sender marginal knowledge is provided.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗