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At least 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Dynamic Matrix Completion Based State Estimation in Distribution Grids

The power distribution network is undergoing tremendous transformation due to an increase in the penetration of renewable energy resources and electric vehicles. These changes have resulted in greater uncertainty and dynamics in the distribution grid states. Therefore, the ability to track and monitor system states has become a critical need for accurate and timely control actions. In this paper, we propose two dynamic sparsity-based state estimation approaches for distribution systems: (1) locally weighted matrix completion (LW-MC) and (2) Bayesian matrix completion with Kalman filter prediction (BMC-KF). The performance of the proposed dynamic state estimation strategies is compared with the classic/static matrix completion (static-MC) approach using the IEEE 37 and IEEE 123 bus test systems. Finally, results indicate that BMC-KF approach outperforms both LW-MC as well as static-MC even when 30% of the measurement data is available. Computational complexity associated with both approaches is quantified.

42 ENGINEERING↗
DOE OSTI2016

Completion Report for Well ER-20-12: Corrective Action Units 101 and 102: Central and Western Pahute Mesa

Well ER-20-12 was drilled for the U.S. Department of Energy, Nevada National Security Administration Nevada Field Office in support of the Underground Test Area Activity. The well was drilled from October 2015 to January 2016 as an addition to the Central and Western Pahute Mesa corrective action units 101 and 102 the Phase II drilling program. Well ER-20-12 was identified based on recommendations of the Pahute Mesa Guidance Team as a result of anomalous tritium detections in groundwater samples collected from Well PM-3 in 2011 and 2013. The primary purpose of the well was to provide information on the hydrogeology in the area downgradient of select underground tests on Western Pahute Mesa and define hydraulic properties in the saturated Tertiary volcanic rocks. The main 46.99-centimeter (cm) (18.5-inch [in.]) borehole was drilled to a depth of 765.14 meters (m) (2,510.3 ft) and the hole opened to 66.04 cm (26 in.); followed by the 50.80-cm (20-in.) surface casing, which was installed and sealed with cement; and a piezometer (p4) was set in the Timber Mountain welded-tuff aquifer (TMWTA) between the casing and the open borehole. The borehole was continued with a 46.99-cm (18.5-in.) drill bit to a depth of 1,326.53 m (4,352.16 ft), and an intermediate 24.44-cm (9.625-in.) casing was installed and sealed to 1,188.72 m (3,900.00 ft) A piezometer (p3) was installed across the Calico Hills zeolitic composite unit (CHZCM) (lava-flow aquifer [LFA]) in the annulus of the open borehole. Two additional piezometers were installed and completed between the intermediate casing and the borehole wall, one (p2) in the CHZCM and one (p1) in the Belted Range aquifer (BRA). The piezometers are set to monitor groundwater properties in the completed intervals. The borehole was continued with a 21.59-cm (8.5-in.) drill bit to a total depth of 1,384.80 m (4,543.33 ft), and the main completion 13.97-cm (5.5-in.) casing was installed in the open borehole across the Pre-Belted Range composite unit (PBRCM). Data collected during hole construction include composite drill cutting samples collected every 3.0 m (10 ft), geophysical logs, hydrophysical logs, percussion core samples, water-quality measurements (including tritium), and water-level measurements. The well penetrated 1,384.4 m (4,543.33 ft) of Tertiary volcanic rocks. The stratigraphy and lithology were generally as expected with one noted exception. A thick lava-flow and related ash-flow tuffs were identified as Calico Hills Formation (Th), and no Crater Flat units were noted. Additionally, many of the Thirsty Canyon and Timber Mountain units were thicker than expected. Fluid levels measured in the borehole during drilling are the following: (1) on November 2, 2015, Navarro measured the fluid level in the borehole at a depth of 492.33 m (1,615.25 ft) below ground surface (bgs); (2) Schlumberger and COLOG recorded fluid levels during geophysical logging on November 4 and 5, 2015, at a depth of 492.86 m (1,617 ft) and 492.25 m (1,615 ft) bgs, respectively; and (3) on December 4, 2015, COLOG and Navarro measured fluid level in the 20-in. casing with an open borehole to 1,326.54 m (4,352.16 ft) bgs at 575.77 m (1,889.00 ft) and 574.03 m (1,883.3 ft) bgs, respectively. These and subsequent water-level measurements indicate a potential head difference of greater than 76.2 m (250 ft) for groundwater in aquifers above and below the Upper Paintbrush confining unit (UPCU). As expected, tritium was occasionally measured above the Safe Drinking Water Act limit (20,000 picocuries per liter [pCi/L]). Lab analysis on four bailed samples and taken from the undeveloped well indicate that the tritium activities average approximately 36,545 pCi/L. All Fluid Management Plan (FMP) requirements for Well ER-20-12 were met. Analysis of monitoring samples and FMP confirmatory samples indicate that fluids generated during drilling at ER-20-12 met the FMP criteria for discharge to the lined sump and designated infiltration area. All sanitary and hydrocarbon waste generated was properly handled and disposed of.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2017

Completion Report for Well ER-4-1 Corrective Action Unit 97: Yucca Flat/Climax Mine, Revision 0

Well ER-4-1 was drilled for the U.S. Department of Energy, Nevada National Security Administration Nevada Field Office in support of the Underground Test Area (UGTA) Activity. The well was drilled and completed from March 23 to April 13, 2016, as part of the Corrective Action Investigation Plan (CAIP) for Yucca Flat/Climax Mine Corrective Action Unit (CAU) 97. The primary purpose of the well was to collect hydrogeologic data to assist in validating concepts of the groundwater flow system within the Yucca Flat/Climax Mine CAU, and to test for potential radionuclides in groundwater from the STRAIT (U4a) underground test. The completed well includes one piezometer (p1), to a depth of 663.16 meters (m) (2,175.71 feet [ft]) below ground surface (bgs) and open from the Alluvial aquifer (AA3) to the Oak Spring Butte confining unit (OSBCU) hydrostratigraphic units; and a main completion (m1), which includes 6.625-inch (in.) casing with slotted interval (m1) installed to 906.80 m (2,975.05 ft) bgs in the Lower carbonate aquifer (LCA). A 13.375-in. diameter surface casing was installed from the surface to a depth of 809.00 m (2,654.21 ft) bgs. Well ER-4-1 experienced a number of technical issues during drilling, including borehole instability and sloughing conditions. An intermediate, 10.75-in./9.625-in. casing string was installed to 856.94 m (2,811.48 ft) bgs to control these issues. Borehole stability and erosion problems appear to be associated with the Tunnel Formation (Tn) and the Older tunnel beds (Ton). Overall efforts to stabilize the borehole were successful. Data collected during borehole construction include composite drill cutting samples collected every 3.0 m (10 ft), a partial suite of geophysical logs to a maximum depth of 766.57 m (2,515 ft) bgs, water-quality measurements (including tritium), water-level measurements, and two depth-discrete bailer samples collected at 538.89 m and 646.18 m (1,768 ft and 2,120 ft) bgs respectively. The well penetrated 187.45 m (615 ft) of Quaternary/Tertiary alluvium (QTa), 671.47 m (2,203 ft) of Tertiary Volcanic rocks (Tv), and 66.20 m (217.19 ft) of Paleozoic rocks (|). The stratigraphy and lithology were generally as expected with some exceptions. The top of Paleozoic rocks (|) was predicted to occur at 822.35 m (2,698 ft) bgs and was intercepted at 858.93 m (2,818 ft), a difference of 36.58 m (120 ft). As expected, the Paleozoic rocks (|) are the principal water producing formation in Well ER-4-1. Depth to water was measured after drilling as follows: In the piezometers: p1 at 320.39 m (1,051.16 ft) bgs, (measured January 4, 2017); and in the main production casing interval: m1 at 539.17 m (1,768.92 ft) bgs, (measured December 12, 2016) Geophysical logs and depth-discrete bailer sample analytical results suggest likely zones of prompt injection (underground-test-related) fission products from 472.44 to 481.48 m (1,550 to 1,580 ft) bgs and at approximately 539.50 m (1,770 ft) bgs. Subsequent work at Well ER-4-1 will be included in future reports. Field measurements for tritium were mostly below the Safe Drinking Water Act limit (20,000 picocuries per liter) with the exception of two zones showing elevated tritium concentrations. The first zone is located at approximately 365.76 to 390.14 m (1,200 to 1,280 ft) bgs and a second zone at approximately 542.54 to 566.93 m (1,780 to 1,860 ft) bgs. All Fluid Management Plan requirements were met.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2019

State Estimation in Low-Observable Distribution Systems Using Matrix Completion: Preprint

The need for distribution system state estimation is on the rise because of the increased penetration of distributed energy resources and flexible load. To manage the distribution systems in real time, operators need to first overcome the challenge of low observability in distribution systems. Also, because of the amount of data present from smart meters, distributed generation measurements, switches, etc., the ideal distribution state estimation methods need to be able to process heterogeneous data. In this paper, an algorithm is developed for voltage phasor estimation in low-observability distribution systems. The algorithm is based on the matrix completion approach from signal processing. The traditional matrix completion formulation is augmented with power-flow constraints to improve results while requiring less data. This method can also use all types of measurements (voltage magnitude, voltage angle, real power, reactive power) to complete the state matrix.

24 POWER TRANSMISSION AND DISTRIBUTION↗
DOE OSTI2019

Sample Complexity of Power System State Estimation using Matrix Completion: Preprint

In this paper, we propose an analytical framework to quantify the amount of data samples needed to obtain accurate state estimation in a power system-a problem known as \emph{sample complexity} analysis in computer science. Motivated by the increasing adoption of distributed energy resources into the distribution-level grids, it becomes imperative to estimate the state of distribution grids in order to ensure stable operation. Traditional power system state estimation techniques mainly focus on the transmission network which involve solving an overdetermined system and eliminating bad data. However, distribution networks are typically \emph{underdetermined} due to the large number of connection points and high cost of pervasive installation of measurement devices. In this paper, we consider the recently proposed state-estimation method for underdetermined systems that is based on \emph{matrix completion}. In particular, a \emph{constrained} matrix completion algorithm was proposed, wherein the standard matrix completion problem is augmented with additional equality constraints representing the physics (namely power-flow constraints). We analyze the sample complexity of this general method by proving an upper bound on the sample complexity that depends directly on the properties of these constraints that can lower number of needed samples as compared to the unconstrained problem. To demonstrate the improvement that the constraints add to state estimation, we test the method on a 141-bus distribution network case study and compare it to the traditional least squares minimization state estimation method.

24 POWER TRANSMISSION AND DISTRIBUTION↗
DOE OSTI2019

Robust Matrix Completion State Estimation in Distribution Systems: Preprint

Due to the insufficient measurements in the distribution system state estimation (DSSE), full observability and redundant measurements are difficult to achieve without using the pseudo measurements. The matrix completion state estimation (MCSE) combines the matrix completion and power system model to estimate voltage by exploring the low-rank characteristics of the matrix. This paper proposes a robust matrix completion state estimation (RMCSE) to estimate the voltage in a distribution system under a low-observability condition. Tradition state estimation weighted least squares (WLS) method requires full observability to calculate the states and needs redundant measurements to proceed a bad data detection. The proposed method improves the robustness of the MCSE to bad data by minimizing the rank of the matrix and measurements residual with different weights. It can estimate the system state in a low-observability system and has robust estimates without the bad data detection process in the face of multiple bad data. The method is numerically evaluated on the IEEE 33-node radial distribution system. The estimation performance and robustness of RMCSE are compared with the WLS with the largest normalized residual bad data identification (WLS-LNR), and the MCSE.

24 POWER TRANSMISSION AND DISTRIBUTION↗
DOE OSTI2016

Filling in the GAPS: evaluating completeness and coverage of open-access biodiversity databases in the United States

Primary biodiversity data constitute observations of particular species at given points in time and space. Open-access electronic databases provide unprecedented access to these data, but their usefulness in characterizing species distributions and patterns in biodiversity depend on how complete species inventories are at a given survey location and how uniformly distributed survey locations are along dimensions of time, space, and environment. Our aim was to compare completeness and coverage among three open-access databases representing ten taxonomic groups (amphibians, birds, freshwater bivalves, crayfish, freshwater fish, fungi, insects, mammals, plants, and reptiles) in the contiguous United States. We compiled occurrence records from the Global Biodiversity Information Facility (GBIF), the North American Breeding Bird Survey (BBS), and federally administered fish surveys (FFS). In this study, we aggregated occurrence records by 0.1° × 0.1° grid cells and computed three completeness metrics to classify each grid cell as well-surveyed or not. Next, we compared frequency distributions of surveyed grid cells to background environmental conditions in a GIS and performed Kolmogorov–Smirnov tests to quantify coverage through time, along two spatial gradients, and along eight environmental gradients. The three databases contributed >13.6 million reliable occurrence records distributed among >190,000 grid cells. The percent of well-surveyed grid cells was substantially lower for GBIF (5.2%) than for systematic surveys (BBS and FFS; 82.5%). Still, the large number of GBIF occurrence records produced at least 250 well-surveyed grid cells for six of nine taxonomic groups. Coverages of systematic surveys were less biased across spatial and environmental dimensions but were more biased in temporal coverage compared to GBIF data. GBIF coverages also varied among taxonomic groups, consistent with commonly recognized geographic, environmental, and institutional sampling biases. Lastly, this comprehensive assessment of biodiversity data across the contiguous United States provides a prioritization scheme to fill in the gaps by contributing existing occurrence records to the public domain and planning future surveys.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2016

Percutaneous Transluminal Angioplasty for Complete Membranous Obstruction of Suprahepatic Inferior Vena Cava: Long-Term Results

PurposeTo determine the long-term results of percutaneous transluminal angioplasty (PTA) for a complete membranous obstruction of the suprahepatic inferior vena cava.MethodsPatients (n = 65) who were referred to the interventional unit for PTA for a complete membranous obstruction of the suprahepatic inferior vena cava between January 2006 and October 2014 were included in the study. Thirty-two patients (18 males, 14 females, mean age 35 ± 10.7, range 20–42 years) were treated. The patients presented with symptoms of ascites (88 %), pleural effusion (53 %), varicose veins (94 %), hepatomegaly (97 %), abdominal pain (84 %), and splenomegaly (40 %). Transjugular liver access set and re-entry catheter were used to puncture and traverse the obstruction from the jugular side. PTA balloon dilations were performed. The mean follow-up period was 65.6 ± 24.5 months. The objective was to evaluate technical success, complications, primary patency, and clinical improvement in the symptoms of the patients.ResultsThe technical success rate was 94 %. In two patients, obstruction could not be traversed. These patients underwent cavoatrial graft bypass surgery. There were no procedure-related complications. Clinical improvements were achieved in all patients within 3 months. The primary patency rate at 4 years was 90 %. There was no primary assisted patency. There was no need for metallic stent deployment in the cohort. The secondary patency rate at 4 years was 100 %.ConclusionsPercutaneous transluminal angioplasty for a complete membranous obstruction of the suprahepatic inferior vena cava is safe and effective, and the long-term results are excellent.

62 RADIOLOGY AND NUCLEAR MEDICINE↗
DOE OSTI2014

Complete particle-pair annihilation as a dynamical signature of the spectral singularity

Motivated by the physical relevance of a spectral singularity of interacting many-particle system, we explore the dynamics of two bosons as well as fermions in one-dimensional system with imaginary delta interaction strength. Based on the exact solution, it shows that the two-particle collision leads to amplitude-reduction of the wave function. For fermion pair, the amplitude-reduction depends on the spin configuration of two particles. In both cases, the residual amplitude can vanish when the relative group velocity of two single-particle Gaussian wave packets with equal width reaches the magnitude of the interaction strength, exhibiting complete particle-pair annihilation at the spectral singularity. - Highlights: • We investigate the physical relevance of a spectral singularity. • The two-particle collision leads to amplitude-reduction of the wave function. • There is a singularity spectrum which leads to complete particle-pair annihilation. • Complete particle-pair annihilation can only occur for two distinguishable bosons and singlet fermions. • Pair annihilation provides a detection method of the spectral singularity in the experiment.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2014

Patterns of Local-Regional Failure in Completely Resected Stage IIIA(N2) Non-Small Cell Lung Cancer Cases: Implications for Postoperative Radiation Therapy Clinical Target Volume Design

Purpose: To analyze patterns of local-regional failure (LRF) for completely resected stage IIIA(N2) non-small cell lung cancer (NSCLC) patients treated in our hospital and to propose a clinical target volume (CTV) for postoperative radiation therapy (PORT) in these patients. Methods and Materials: From 2005 to 2011, consecutive patients with pT1-3N2 NSCLC who underwent complete resection in our hospital but who did not receive PORT were identified. The patterns of first LRF were assessed and evaluated as to whether these areas would be encompassed by our proposed PORT CTV. Results: With a median follow-up of 24 months, 173 of 250 patients (69.2%) experienced disease recurrence. Of the 54 patients with LRF as the first event, 48 (89%) had recurrence within the proposed PORT CTV, and 6 (11%) had failures occurring both within and outside the proposed CTV (all of which occurred in patients with right-lung cancer). Ninety-three percent of failure sites (104 of 112) would have been contained within the proposed PORT CTV. For left-sided lung cancer, the most common lymph node station failure site was 4R, followed by 7, 4L, 6, 10L, and 5. For right-sided lung cancer, the most common site was station 2R, followed by 10R, 4R, and 7. Conclusions: LRF following complete surgery was an important and potentially preventable pattern of failure in stage IIIA(N2) patients. Ipsilateral superior mediastinal recurrences dominated for right-sided tumors, whereas left-sided tumors frequently involved the bilateral superior mediastinum. Most of the LRF sites would have been covered by the proposed PORT CTV. A prospective investigation of patterns of failure after PORT (following our proposed CTV delineation guideline) is presently underway and will be reported in a separate analysis.

62 RADIOLOGY AND NUCLEAR MEDICINE↗
DOE OSTI2013

Hyperon Photoproduction from Polarized H and D: towards a complete N* experiment

New complete experiments in pseudoscalar meson photo-production are being pursued at several laboratories. Here the designation of complete refers to measurements of most if not all of the possible reaction observables, of which there are 16 involving spins of the beam, target and recoil baryon. Hyperon production to Λ or Σ{sup +} final states affords attractive opportunities, since their weak decays provide an efficient self-analysis of their polarization. When the beam and target are also polarized, the resulting triple polarization measurements determine the full suite of observables with a single target orientation. This has been a focus at Jefferson Lab in the recently completed g9/FROST and g14/HDice experiments now under analysis. Multipole analyses of γp->K{sup +}Λ have been carried out with a large though incomplete set of recently published polarization data, and the uniqueness of the extracted amplitudes has been studied. Experiments with realistically achievable uncertainties require a significantly greater number of spin asymmetries than the in-principle minimum needed for a mathematical solution of the amplitude.

Baryon resonances↗
DOE OSTI2013

Comparison between lab- and full-scale applications of in situ aeration of an old landfill and assessment of long-term emission development after completion

Highlights: ► Current data on in situ aeration effects from the first Austrian full-scale case study. ► Data on lasting waste stabilisation after aeration completion. ► Information on the transferability of results from lab- to full-scale aeration. - Abstract: Sustainable landfilling has become a fundamental objective in many modern waste management concepts. In this context, the in situ aeration of landfills has been recognised for its potential to convert conventional anaerobic landfills into biological stabilised state, whereby both current and potential (long-term) emissions of the landfilled waste are mitigated. In recent years, different in situ aeration concepts have been successfully applied in Europe, North America and Asia, all pursuing different objectives and strategies. In Austria, the first full-scale application of in situ landfill aeration by means of low pressure air injection and simultaneous off-gas collection and treatment was implemented on an old, small municipal solid waste (MSW) landfill (2.6 ha) in autumn 2007. Complementary laboratory investigations were conducted with waste samples taken from the landfill site in order to provide more information on the transferability of the results from lab- to full-scale aeration measures. In addition, long-term emission development of the stabilised waste after aeration completion was assessed in an ongoing laboratory experiment. Although the initial waste material was described as mostly stable in terms of the biological parameters gas generation potential over 21 days (GP{sub 21}) and respiration activity over 4 days (RA{sub 4}), the lab-scale experiments indicated that aeration, which led to a significant improvement of leachate quality, was accompanied by further measurable changes in the solid waste material under optimised conditions. Even 75 weeks after aeration completion the leachate, as well as gaseous emissions from the stabilised waste material, remained low and stayed below the authorised Austrian discharge limits. However, the application of in situ aeration at the investigated landfill is a factor 10 behind the lab-based predictions after 3 years of operation, mainly due to technical limitations in the full-scale operation (e.g. high air flow resistivity due to high water content of waste and temporarily high water levels within the landfill; limited efficiency of the aeration wells). In addition, material preparation (e.g. sieving, sorting and homogenisation) prior to the emplacement in Landfill Simulation Reactors (LSRs) must be considered when transferring results from lab- to full-scale application.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2025

Modeling Strong Light-Matter Coupling in Correlated Systems: State-Averaged Cavity Quantum Electrodynamics Complete Active Space Self-Consistent Field Theory

The description of strongly correlated systems interacting with quantized cavity modes poses significant theoretical challenges due to the combinatorial scaling of electronic and photonic degrees of freedom. Recent advances addressing this complexity include cavity quantum electrodynamics (QED) generalizations of complete active space configuration interaction and density matrix renormalization group methods. In this work, we introduce a QED extension of state-averaged complete active space self-consistent field theory, which incorporates cavity-induced correlations through a second-order orbital optimization framework with robust convergence properties. The method is implemented using both photon number state and coherent state representations, with the latter showing robust origin invariance in the energies regardless of the completeness of the photonic Fock space. The implementation enables symmetry-free orbital relaxations to account for photon-mediated symmetry breaking in polaritonic systems. Numerical validation on lithium hydride, hydroxide anion, and magnesium hydride cation demonstrates that this method achieves significantly improved accuracy in modeling ground-state and polariton potential energy surfaces compared to QED-CASCI in a fixed orbital basis. In these studies, we reach sub-kcal/mol accuracy in potential energy surface in much smaller active spaces than are required for QED-CASCI. This advancement provides a more robust approach for studying cavity-altered chemical landscapes for ground and exited strongly coupled systems.

CASSCF↗
DOE OSTI2015

Understanding complete oxidation of methane on spinel oxides at a molecular level

It is crucial to develop a catalyst made of earth-abundant elements highly active for a complete oxidation of methane at a relatively low temperature. NiCo 2 O 4 consisting of earth-abundant elements which can completely oxidize methane in the temperature range of 350-550 °C. Being a cost-effective catalyst, NiCo 2 O 4 exhibits activity higher than precious-metal-based catalysts. Here we report that the higher catalytic activity at the relatively low temperature results from the integration of nickel cations, cobalt cations and surface lattice oxygen atoms/oxygen vacancies at the atomic scale. Finally, in situ studies of complete oxidation of methane on NiCo 2 O 4 and theoretical simulations show that methane dissociates to methyl on nickel cations and then couple with surface lattice oxygen atoms to form -CH 3 O with a following dehydrogenation to -CH 2 O; a following oxidative dehydrogenation forms CHO; CHO is transformed to product molecules through two different sub-pathways including dehydrogenation of OCHO and CO oxidation.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Completeness for sparse potential scattering

The present paper is devoted to the scattering theory of a class of continuum Schrödinger operators with deterministic sparse potentials. We first establish the limiting absorption principle for both modified free resolvents and modified perturbed resolvents. This actually is a weak form of the classical limiting absorption principle. We then prove the existence and completeness of local wave operators, which, in particular, imply the existence of wave operators. Under additional assumptions on the sparse potential, we prove the completeness of wave operators. In the context of continuum Schrödinger operators with sparse potentials, this paper gives the first proof of the completeness of wave operators.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Canonical-ensemble state-averaged complete active space self-consistent field (SA-CASSCF) strategy for problems with more diabatic than adiabatic states: Charge-bond resonance in monomethine cyanines

This paper reviews basic results from a theory of the a priori classical probabilities (weights) in state-averaged complete active space self-consistent field (SA-CASSCF) models. It addresses how the classical probabilities limit the invariance of the self-consistency condition to transformations of the complete active space configuration interaction (CAS-CI) problem. Such transformations are of interest for choosing representations of the SA-CASSCF solution that are diabatic with respect to some interaction. I achieve the known result that a SA-CASSCF can be self-consistently transformed only within degenerate subspaces of the CAS-CI ensemble density matrix. For uniformly distributed (“microcanonical”) SA-CASSCF ensembles, self-consistency is invariant to any unitary CAS-CI transformation that acts locally on the ensemble support. Most SA-CASSCF applications in current literature are microcanonical. A problem with microcanonical SA-CASSCF models for problems with “more diabatic than adiabatic” states is described. The problem is that not all diabatic energies and couplings are self-consistently resolvable. A canonical-ensemble SA-CASSCF strategy is proposed to solve the problem. For canonical-ensemble SA-CASSCF, the equilibrated ensemble is a Boltzmann density matrix parametrized by its own CAS-CI Hamiltonian and a Lagrange multiplier acting as an inverse “temperature,” unrelated to the physical temperature. Like the convergence criterion for microcanonical-ensemble SA-CASSCF, the equilibration condition for canonical-ensemble SA-CASSCF is invariant to transformations that act locally on the ensemble CAS-CI density matrix. The advantage of a canonical-ensemble description is that more adiabatic states can be included in the support of the ensemble without running into convergence problems. The constraint on the dimensionality of the problem is relieved by the introduction of an energy constraint. The method is illustrated with a complete active space valence-bond (CASVB) analysis of the charge/bond resonance electronic structure of a monomethine cyanine: Michler’s hydrol blue. The diabatic CASVB representation is shown to vary weakly for “temperatures” corresponding to visible photon energies. Canonical-ensemble SA-CASSCF enables the resolution of energies and couplings for all covalent and ionic CASVB structures contributing to the SA-CASSCF ensemble. The CASVB solution describes resonance of charge- and bond-localized electronic structures interacting via bridge resonance superexchange. The resonance couplings can be separated into channels associated with either covalent charge delocalization or chemical bonding interactions, with the latter significantly stronger than the former.

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

Discontinuities-free complete-active-space state–specific multi–reference coupled cluster theory for describing bond stretching and dissociation

The earlier proposed multi-reference state-specific coupled-cluster theory with the complete active space reference suffered from a problem of energy discontinuities when the formal reference state was changing in the calculation of the potential energy curve (PEC). A simple remedy to the discontinuity problem is found and is presented in this work. It involves using natural complete active space self-consistent field active orbitals in the complete active space coupled-cluster calculations. As a result, the approach gives smooth PECs for different types of dissociation problems, as illustrated in the calculations of the dissociation of the single bond in the hydrogen fluorine molecule and of the symmetric double-bond dissociation in the water molecule.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗