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At least 19 records

Spin contamination in unrestricted Hartree-Fock calculations.

Several pi-electron doublets are treated by both the unrestricted Hartree-Fock method and the restricted approximation of Longuet-Higgins and Pople. For two of the molecules, which contain oxygen heteroatoms, serious spin contamination occurs in the UHF wavefunctions, and this negates the usefulness of the single annihilation procedure that is often used for spin-density calculations. The restricted approximation provides a convenient alternative, especially because configuration interaction is easily taken into account.

Schug, J. C.↗

The approximate second order coupled-cluster method based on a size-consistent Brillouin–Wigner partitioning

We present a variant of the approximate second order coupled-cluster method (CC2) with a two-parameter size-consistent Brillouin–Wigner (BW-s) partitioning instead of a Møller–Plesset (MP) partitioning for the unperturbed Hamiltonian, which we refer to as BWs-CC2. The computational complexity of this model scales identically to CC2 with molecular size. Conventional CC2 and its regularized BWs-CC2 variants, as well as conventional MP2 and two of its regularized BW-s2 variants, were assessed on a 535 element database spanning thermochemistry, non-covalent interactions, barrier heights, and isomerization energies. To ensure a well-defined model chemistry, the assessment was performed using internally stable spin-polarized Hartree–Fock (HF) orbitals in the finite aug-cc-pVQZ basis without counterpoise corrections. As a result of using stable orbitals, contrary to conventional wisdom, we find that CC2 substantially outperforms MP2 on molecules with significantly spin contaminated reference orbitals without a significant increase in error on systems with a spin-pure reference, showing the value of its single substitutions. While no single choice of regularization parameters can be optimal for all datasets, we find that BWs-CC2 generally outperforms both CC2 and BW-s2 with a single judicious parameter choice. Additional tests on dipole moments and bond lengths of diatomics provide further support for the utility of this choice. Furthermore, the main outliers and poorest performing cases are associated with large amounts of spin-contamination in the HF reference, which is indicative of systems with either strong correlation or extensive artificial symmetry breaking. Overall, these findings argue that the perception of the quality of the CC2 ground state should be reevaluated and that it can be further improved upon by the soundly based BWs-CC2 variant with the recommended parameter choice.

Correlation energy↗

Computation of the expectation value of the spin operator S^ 2 for the spin-flip Bethe–Salpeter equation

Spin-flip (SF) methods applied to excited-state approaches like the Bethe–Salpeter equation allow access to the excitation energies of open-shell systems, such as molecules and defects in solids. The eigenstates of these solutions, however, are generally not eigenstates of the spin operator S^ 2 . Even for simple cases where the excitation vector is expected to be, for example, a triplet state, the value of S^ 2 may be found to differ from 2.00; this difference is called 'spin contamination'. The expectation values S^ 2 must be computed for each excitation vector, to assist with the characterization of the particular excitation and to determine the amount of spin contamination of the state. Here, our aim is to provide for the first time in the SF methods literature a comprehensive resource on the derivation of the formulas for S^ 2 as well as its computational implementation. After a brief discussion of the theory of the SF Bethe–Salpeter equation (BSE) and some examples further illustrating the need for calculating S^ 2 , we present the derivation for the general equation for computing S^ 2 with the eigenvectors from an SF-BSE calculation, how it is implemented in a Python script, and timing information on how this calculation scales with the size of the SF-BSE Hamiltonian.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

The cosine-sine decomposition with different-orbitals-for-different-spins determinants

We report the spin decomposition of a spin-contaminated different-orbitals-for-different-spins (DODS) wave function is formulated in terms of the Krylov space of the $\hat{S}^2$ ||operator. The number of determinants that contribute to the various projected spin eigenfunctions vertical | $\psi ; S, M \rangle$ depends on the sparsity of the orbital overlap matrix X between the α and β spatial orbitals. The cosine-sine decomposition (CSD) procedure may be applied to this overlap matrix, and the resulting redundant orbital transformations may be applied to the α and β spatial orbitals. This produces a sparse X' matrix in the transformed basis in which each row or column has either one or two nonzero elements. This sparse X' matrix simplifies the spin-decomposition procedure in three ways:1) it reduces the number of contributing determinants within the Krylov basis functions and within the projected spin functions, 2) it reduces the effective orbital dimension through elimination of the frozen core and frozen virtual orbitals, and 3) it simplifies the spin-decomposition procedure in both the original and transformed bases by limiting the Krylov space dimension. These simplifications all reduce the computational effort for the spin-decomposition process. This procedure is implemented within a string-based DODS determinant formulation and applied to spin projection of unrestricted Hartree-Fock determinants.

unrestricted Hartree-Fock↗

Accurate core excitation and ionization energies from a state-specific coupled-cluster singles and doubles approach

Here, we investigate the use of orbital-optimized references in conjunction with single-reference coupled-cluster theory with single and double substitutions (CCSD) for the study of core excitations and ionizations of 18 small organic molecules, without the use of response theory or equation-of-motion (EOM) formalisms. Three schemes are employed to successfully address the convergence difficulties associated with the coupled-cluster equations, and the spin contamination resulting from the use of a spin symmetry-broken reference, in the case of excitations. In order to gauge the inherent potential of the methods studied, an effort is made to provide reasonable basis set limit estimates for the transition energies. Overall, we find that the two best-performing schemes studied here for ΔCCSD are capable of predicting excitation and ionization energies with errors comparable to experimental accuracies. The proposed ΔCCSD schemes reduces statistical errors against experimental excitation energies by more than a factor of two when compared to the frozen-core core–valence separated (FC-CVS) EOM-CCSD approach – a successful variant of EOM-CCSD tailored towards core excitations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Open-Shell Tensor Hypercontraction

The extension of least-squares tensor hypercontracted second- and third-order Møller–Plesset perturbation theory (LS-THC-MP2 and LS-THC-MP3) to open-shell systems is an important development due to the scaling reduction afforded by THC and the ubiquity of molecular ions, radicals, and other open-shell reactive species. The complexity of wavefunction-based quantum-chemical methods such as Møller–Plesset and coupled cluster theory is reflected in the steep scaling of the computational costs with the molecular size. The least-squares tensor hypercontraction (LS-THC) method is an efficient, single-step factorization for the two-electron integral tensor but can also be used to factorize the double excitation amplitudes, leading to significant scaling reduction. Herein we extend this promising method to open-shell variants of LS-THC-MP2 and -MP3 by using diagrammatic techniques and explicit spin summation. The accuracy of the resulting methods for open-shell species is benchmarked on standard test systems such as regular alkanes as well as realistic systems involving bond breaking, radical stabilization, and other effects. We find that open-shell LS-THC-MPn methods exhibit errors highly comparable to those produced by closed-shell LS-THC-MPn and are highly insensitive to particular chemical interactions, geometries, or even moderate spin contamination.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Gold-Standard Chemical Database 137 (GSCDB137): A Diverse Set of Accurate Energy Differences for Assessing and Developing Density Functionals

We present GSCDB137, a rigorously curated benchmark library of 137 data sets (8377 entries) covering main-group and transition-metal reaction energies and barrier heights, (intra- and intermolecular) noncovalent interactions, dipole moments, polarizabilities, electric-field response energies, and vibrational frequencies. Legacy data from GMTKN55 and MGCDB84 have been updated to today's best reference values; redundant or low-quality points were removed, and many new, property-focused sets were added. Testing 29 popular density functional approximations (DFAs) confirms the expected Jacob's-ladder hierarchy overall but also reveals notable exceptions: functional performance for frequencies and electric-field properties correlates poorly with that for other ground-state energetics. ωB97M-V and ωB97X-V are the most balanced hybrid meta-GGA and hybrid GGA, respectively; B97M-V and revPBE-D4 lead the meta-GGA and GGA classes. Double hybrids lower mean errors by about 30% versus their hybrid analogues but demand careful frozen-core, basis set, and spin contamination treatment. GSCDB137 offers a comprehensive, openly documented platform for rigorous validation of DFA and universal machine learning potentials, and training of the next generation of exchange-correlation functionals.

Liang, Jiashu [University of California, Berkeley,↗

Recent Advances in Open-Shell Perturbation Theory and Coupled-Cluster Theory

Comparisons of various recently developed open-shell RHF perturbation theories will be presented. Among the aspects considered are spin-contamination, computational cost, and quality of numerical results. In addition, a new approach to avoid the disk storage and I/O bottlenecks in large scale coupled-cluster calculations will be discussed.

Lee, Timothy J.↗

High-performance strategies for the recent MRSF-TDDFT in GAMESS

Multiple ERI (Electron Repulsion Integral) tensor contractions (METC) with several matrices are ubiquitous in quantum chemistry. In response theories, the contraction operation, rather than ERI computations, can be the major bottleneck, as its computational demands are proportional to the multiplicatively combined contributions of the number of excited states and the kernel pre-factors. Here, this paper presents several high-performance strategies for METC. Optimal approaches involve either the data layout reformations of interim density and Fock matrices, the introduction of intermediate ERI quartet buffer, and loop-reordering optimization for a higher cache hit rate. The combined strategies remarkably improve the performance of the MRSF (mixed reference spin flip)-TDDFT (time-dependent density functional theory) by nearly 300%. The results of this study are not limited to the MRSF-TDDFT method and can be applied to other METC scenarios.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Galileo spin rate control

This paper presents the analysis and design of the spin rate control flight algorithm for the dual-spin Galileo spacecraft. Because of thruster plume contamination constraints, only one poorly located thruster is available for spin rate correction in each spin direction. Hence, firing of any of the spin thrusters has a deleterious effect on spacecraft pointing. A control strategy was developed for achieving the desired spin rate correction while keeping disturbances at acceptable levels. This involved symmetrically distributed multiple thruster burns. Results of extensive tests of the adopted scheme on a computer simulation of the spacecraft are also presented.

Eke, F. O.↗

Spin diffusion in the Phosphorus-31 NMR relaxation in a layered crystalline α-Sn(IV) phosphate contaminated by paramagnetic impurities

The study of a layered crystalline Sn(IV) phosphate by solid-state NMR has demonstrated that the 31 P T 1 relaxation of phosphate groups, dependent on spinning rate is completely controlled by the limited spin diffusion to paramagnetic ions found by EPR. The spin-diffusion constant, D(SD), was estimated as 2.04 10 –14 cm 2 s –1 . Finally, the conclusion was supported by the 31 P T 1 time measurements in zirconium phosphate 1–1, also showing paramagnetic ions and in diamagnetic compound (NH 4 ) 2 HPO 4 .

1H MAS NMR↗

Genesis Ultrapure Water Megasonic Wafer Spin Cleaner

A device removes, with high precision, the majority of surface particle contamination greater than 1-micron-diameter in size from ultrapure semiconductor wafer materials containing implanted solar wind samples returned by NASA's Genesis mission. This cleaning device uses a 1.5-liter/minute flowing stream of heated ultrapure water (UPW) with 1- MHz oscillating megasonic pulse energy focused at 3 to 5 mm away from the wafer surface spinning at 1,000 to 10,000 RPM, depending on sample size. The surface particle contamination is removed by three processes: flowing UPW, megasonic cavitations, and centripetal force from the spinning wafer. The device can also dry the wafer fragment after UPW/megasonic cleaning by continuing to spin the wafer in the cleaning chamber, which is purged with flowing ultrapure nitrogen gas at 65 psi (.448 kPa). The cleaner also uses three types of vacuum chucks that can accommodate all Genesis-flown array fragments in any dimensional shape between 3 and 100 mm in diameter. A sample vacuum chuck, and the manufactured UPW/megasonic nozzle holder, replace the human deficiencies by maintaining a consistent distance between the nozzle and wafer surface as well as allowing for longer cleaning time. The 3- to 5-mm critical distance is important for the ability to remove particles by megasonic cavitations. The increased UPW sonication time and exposure to heated UPW improve the removal of 1- to 5-micron-sized particles.

Allton, Judith H.↗

Large–scale asymmetry in galaxy spin directions: Analysis of galaxies with spectra in DES, SDSS, and DESI Legacy Survey

Multiple previous studies using several different probes have shown considerable evidence for the existence of cosmological–scale anisotropy and a Hubble–scale axis. One of the probes that show such evidence is the distribution of the directions toward which galaxies spin. The advantage of the analysis of the distribution of galaxy spin directions compared to the cosmic microwave background anisotropy is that the ratio of galaxy spin directions is a relative measurement, and therefore less sensitive to background contamination such as Milky Way obstruction. Another advantage is that many spiral galaxies have spectra, and therefore allow to analyze the location of such axis relative to Earth. This paper shows an analysis of the distribution of the spin directions of over 90K galaxies with spectra. That analysis is also compared to previous analyses using the Earth–based Sloan Digital Sky Survey, Panoramic Survey Telescope and Rapid Response System, and Dark Energy Spectroscopic Instrument Legacy Survey, as well as space–based data collected by Hubble Space Telescope. Finally, the results show very good agreement between the distribution patterns observed with the different telescopes. The dipole or quadrupole axes formed by the spin directions of the galaxies with spectra do not necessarily go directly through Earth.

79 ASTRONOMY AND ASTROPHYSICS↗

Probing intrinsic magnetization dynamics of the Y 3⁢ Fe 5 ⁢O 12 /Bi 2 ⁢Te 3 interface at low temperature

Topological insulator–magnetic insulator (TI–MI) heterostructures hold significant promise in the field of spintronics, offering the potential for manipulating magnetization through topological surface state–enabled spin-orbit torque. However, many TI–MI interfaces are plagued by issues such as contamination within the magnetic insulator layer and the presence of a low-density transitional region of the topological insulator. These interfacial challenges often obscure the intrinsic behavior of the TI–MI system. In this study, we addressed these challenges by depositing sputtered Bi 2 ⁢Te 3 on liquid phase epitaxy grown Y 3 ⁢Fe 5 ⁢O 12 /Gd 3 ⁢Ga 5 ⁢O 12 . The liquid phase epitaxy grown Y 3 ⁢Fe 5 ⁢O 12 has been previously shown to have exceptional interface quality, without an extended transient layer derived from interdiffusion processes of the substrate or impurity ions, thereby eliminating rare-earth impurity-related losses in the MI at low temperatures. At the TI–MI interface, high-resolution depth-sensitive polarized neutron reflectometry confirmed the absence of a low-density transitional growth region of the TI. By overcoming these undesirable interfacial effects, we isolate and probe the intrinsic low-temperature magnetization dynamics and transport properties of the TI–MI interface. In conclusion, our findings revealed strong spin pumping at low temperatures, accompanied by an additional in-plane anisotropy. The enhanced spin pumping at low temperatures is correlated with the observed suppression of bulk conduction and the weak antilocalization in the TI film, highlighting the interplay between the transport and spin pumping behavior in the TI–MI system.

36 MATERIALS SCIENCE↗

Maneuver Design and Calibration for the Genesis Spacecraft

Genesis is the fifth mission selected as part of NASA's Discovery Program. The objective of Genesis is to collect solar wind samples for a period of approximately two years while in a halo orbit about the Earth-Sun L I point. At the end of this period, the samples are to be returned to a specific recovery point on the Earth for subsequent analysis. This goal has never been attempted before and presents a formidable challenge in terms of mission design and operations, particularly planning and execution of propulsive maneuvers. To achieve a level of cost-effectiveness consistent with a Discovery-class mission, the Genesis spacecraft design was adapted to the maximum extent possible from designs used on earlier missions, such as Mars Global Surveyor (MGS) and Stardust, another sample collection mission. The spacecraft design for Genesis is shown. Spin stabilization was chosen for attitude control, in lieu of three-axis stabilization, with neither reaction wheels nor accelerometers included. This precludes closed-loop control of propulsive maneuvers and implies that any attitude changes, including spin changes and precessions, will behave like translational propulsive maneuvers and affect the spacecraft trajectory. Moreover, to minimize contamination risk to the samples collected, all thrusters were placed on the side opposite the sample collection canister. The orientation and characteristics of thrusters are indicated. For large maneuvers (>2.5 m/s), two 5 lbf thrusters will be used for delta v, with precession to the burn attitude, followed by spin-up from 1.6 to 10 rpm before the burn and spin down to 1.6 rpm afterwards, then precession back to the original spin attitude. For small maneuvers (<2.5 m/s), no spin change is needed and four 0.2 lbf thrusters are used for Av. Single or double 360 deg. precession changes are required whenever the desired delta v falls inside the two-way turn circle (about 0.4 m/s) based on the mass properties, spin rate and lever arm lengths based on thruster locations. In such instances, delta v resulting from spacecraft precession cannot be used effectively as a component of the desired delta v, and must therefore be removed by precessing at least one complete revolution around the turn circle. To eliminate cross-track execution errors, a second revolution in the opposite direction would also be performed. This paper will address the design of propulsive maneuvers in light of the aforementioned challenges and other constraints. Maneuver design will be performed jointly by the Navigation Team at JPL and the Spacecraft Team at LMA, based on the process indicated . Typical maneuver timelines will be presented which address considerations introduced by attitude changes. These include nutation, which is introduced by precessing or spinning down and must be given sufficient time to damp out prior to execution of subsequent events, as well as sun and earth pointing constraints, which must be considered to ensure sufficient spacecraft power and to minimize telecommunications interruptions, respectively. The paper will include a description of how individual propulsive maneuvers are resolved into components to account for delta v from translational burns and spacecraft attitude changes required to carry out such maneuvers. Contributions to maneuver delta v arising from attitude changes, based on mass properties for the period just after launch, are indicated. Similar curves will be presented spanning all mission phases from launch through return. A set of closed-form equations for resolving maneuver components, base on a specific delta v required for correction or deterministic changes to the spacecraft trajectory will be presented, as well. In addition to nominal maneuvers, special calibration maneuvers are planned to improve open-loop modeling of maneuvers and to reduce execution errors. Uncalibrated execution errors are indicated. Such errors could be reduced by 50% or more over the course of the mission. Special calibrations are of particular importance for the return leg of the mission, since the sample canister must be returned to a specific location within the Utah Test and Training Range (UTTR) for mid-air retrieval. An entry angle tolerance of no less than +/- 0.08 deg. is required to achieve this objective. Biasing of the final return maneuvers coupled with a specific maneuver mode to use a series of well-characterized spin changes to effect these maneuvers is part of the current Genesis baseline mission plan. Another important objective of calibrations is to better characterize precession maneuvers. Such maneuvers are part of most propulsive maneuvers, but are also required periodically to maintain sun-pointing for power or daily during solar-wind pointing during collection periods. Although relatively small, such maneuvers will have a significant cumulative impact on orbit determination, particularly in the halo portion of the mission. The current mission design also calls for three stationkeeping maneuvers during each halo orbit of approximately six months duration. These stationkeeping maneuvers may be sufficiently small that single or double 360 deg. precession changes may be required. Because there are no accelerometers on board the spacecraft, calibration can only be performed with the aid of ground-based radiometric tracking. To establish a high degree of accuracy in characterizing the magnitude of burns, the spacecraft spin axis should be along the line of sight to the Earth, providing Doppler measurements with <1 mm/sec accuracy in S-Band. Emission constraints allow such alignment only during certain portions of the mission when the Earth-spacecraft-sun geometry is favorable. The impact of precessions, or burns at times when geometry is not favorable, can be assessed by reconstruction of the spacecraft trajectory using tracking arcs of several days before and after the event.

Williams, Kenneth E.↗

Genesis Solar Wind Collector Cleaning Assessment: Update on 60336 Sample Case Study

To maximize the scientific return of Genesis Solar Wind return mission it is necessary to characterize and remove a crash-derived particle and thin film surface contamination. A small subset of Genesis mission collector fragments are being subjected to extensive study via various techniques. Here we present an update on the sample 60336, a Czochralski silicon (Si-CZ) based wafer from the bulk array (B/C). This sample has undergone multiple cleaning steps (see the table below): UPW spin wash, aggressive chemical cleanings (including aqua regia, hot xylene and RCA1), as well as optical and chemical (EDS, ToF-SIMS) imaging. Contamination appeared on the surface of 60336 after the initial 2007 UPW cleaning. Aqua regia and hot xylene treatment (8/13/2013) did little to remove contaminants. The sample was UPW cleaned for the third time and imaged (9/16/13). The UPW removed the dark stains that were visible on the sample. However, some features, like "the Flounder" (a large, 100 micron feature in Fig. 1b) appeared largely intact, resisting all previous cleaning efforts. These features were likely from mobilized adhesive, derived from the Post-It notes used to stabilize samples for transport from Utah after the hard landing. To remove this contamination, an RCA step 1 organic cleaning (RCA1) was employed. Although we are still uncertain on the nature of the Flounder and why it is resistant to UPW and aqua regia/hot xylene treatment, we have found RCA1 to be suitable for its removal. It is likely that the glue from sticky pads used during collector recovery may have been a source for resistant organic contamination [9]; however [8] shows that UPW reaction with crash-derived organic contamination does not make particle removal more difficult.

Goreva, Y. S.↗

Moments of nucleon unpolarized, polarized, and transversity parton distribution functions from lattice QCD at the physical point

The second Mellin moments ⟨ x ⟩ of the nucleon’s unpolarized, polarized, and transversity parton distribution functions are computed. Two lattice QCD ensembles at the physical pion mass are used: these were generated using a tree-level Symanzik-improved gauge action and 2 + 1 flavor tree-level improved Wilson Clover fermions coupling via 2-level HEX-smearing. The moments are extracted from forward matrix elements of local leading twist operators. We determine renomalization factors in RI-(S)MOM and match to MS ¯ at scale 2 GeV. Our findings show that operators that exhibit vanishing kinematics at zero momentum can have significantly reduced excited-state contamination. The resulting polarized moment is used to quantify the longitudinal contribution to the quark spin-orbit correlation. All our results agree within two sigma with previous lattice results. Published by the American Physical Society 2024

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗