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DOE OSTI2016

Preparatory Verification of a New Monte Carlo Code cosRMC based on VERA Core Physics Benchmark

To promote nuclear power plant system design and simulation software self-reliance development, DOE of China approved a R and D key project to develop an integrated engine for pressurized water reactor core and system design and analysis, referred as COSINE hereafter. The scope of this code package includes reactor physics, thermal hydraulics, safety analysis, severe accidents, probability safety assessment and etc. Many universities, research institutes and nuclear related corporations in China are involved in the code development, among which the State Nuclear Power Software Development Center (SNPSDC) plays the leading role. With the requirement of accurate three-dimensional modeling of the advanced, special or new complex core in reactor neutronics and shielding analysis, Monte Carlo method is becoming a more powerful tool for reactor analysis. Thus, a new Monte Carlo transport code named cosRMC (abbreviation for COSINE Reactor Monte Carlo) has been developed jointly by SNPSDC and Department of Engineering Physics, Tsinghua University, the main developer of RMC code. The cosRMC now has many functions as criticality calculation, fixed-source calculation, burnup calculation, and etc. Some techniques for geometry treatment, new burnup algorithm, source convergence acceleration, massive tally and parallel calculation have been implemented in cosRMC to improve the efficiency. In order to ensure its reliability, several types of V and V work have been and are being carried out for cosRMC. In this paper, some preparatory verification results based on VERA Core Physics Benchmark are presented. (authors)

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

DOE OSTI2017

Analysis of the VERA Core Physics Benchmark Problems using cosRMC Code

In reactor physics, two kinds of numerical methods are generally employed to solve the neutron transport equations, one of which is the deterministic method and the other one is the Monte Carlo method. Monte Carlo is widely used to provide reference solution because of its ability to deal with continuous energy cross sections and complex geometry. Just like any statistical process, the Monte Carlo method requires repetition to achieve a small relative uncertainty, and therefore may inevitably have larger simulation times than deterministic method. Fortunately, the great advancements of computer technology make it possible to apply Monte Carlo method in reactor core analysis. To promote nuclear power plant system design and simulation software self-reliance development, a Monte Carlo neutron/photon transport code cosRMC has been developed jointly by State Nuclear Power Software Development Center (SNPSDC) and Tsinghua University. The cosRMC is aimed at achieving full core calculations and analysis with high fidelity and efficiency by means of advanced methodologies and algorithms as well as high performance computing techniques. The cosRMC has many functions as criticality calculation, fixed-source calculation, burnup calculation, etc. In order to ensure its reliability, several types of verification and validation (V and V) work have been and are being carried out for cosRMC. The simulation results of cosRMC based on Problem 1 to 3 of VERA Core Physics Benchmark showed its good capability of 2D lattice and 3D assembly modeling. In this paper, some progressive verification results of multi-assembly and full core problems are presented.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

DOE OSTI2024

Addressing Consequence within Operational Risk (O.T. Gagnon III) 9-18-2024

Addressing Consequence within Operational Risk: Why threats and security are just not that important! When dealing with cyber or physical risk within any critical infrastructure (CI) environment, don’t concern yourself with vulnerabilities and threats, at least not at first! Also, don’t be overly fixated on “securing the systems” within the organization. The endeavor of tackling operational risk focused on consequences in any critical infrastructure environment to include the complex Aviation ecosystem is challenging even for the most resourced entity but can be advanced though a simplified approach: identifying, binning, and prioritizing the infrastructure environment. While no two entities within a single element of the 16 critical infrastructure sectors are exactly alike when it comes to risk, there is a basic process to move toward a greater understanding of operational risk through becoming more informed about the infrastructure environment in which the entity exists. The process starts with bringing internal and external stakeholders and subject matter experts together to analyze key areas such as Information Technology (IT) and Operational Technology (OT) components and points of convergence, analyzing internal and external cyber and physical dependencies, accounting for explosive growth in devices and wireless technology, and leveraging the contributions of people inside and outside the operational environment. Attaining a common understanding of the infrastructure environment as part of addressing consequences within operational risk is not easy to do or resource light, but the process outlined provides the framework to further any entity’s efforts in this space. When it comes to cyber risks, before an organization can consider vulnerabilities within and threats to its operations, it must first have a solid understanding of the consequences existing inside its infrastructure environment. Idaho National Lab’s Consequence-Driven, Cyber-Informed Engineering is offered as an example of this approach to effective and efficient cyber risk mitigation.

99 GENERAL AND MISCELLANEOUS↗

DOE OSTI2025

Determining Drying Conditions to Mitigate Hanford Transfer Line Corrosion

Radioactive waste is stored in underground, carbon-steel double-shell tanks at the Department of Energy Hanford site.1,2,3 The underground transfer lines are used to transfer the waste between the tanks and other assets at the Hanford tank farm facilities. The transfer lines constructed before 1990 are pipe-in-pipe design with most of the lines having carbon steel carrier pipe and carbon steel encasements. The lines constructed after 1990 have a stainless-steel carrier with a carbon steel encasement. The carrier lines, which are in contact with the waste, provide a critical confinement function, while the encasements provide secondary containment to reduce the risk of a release and contamination to the environment. In 2022, a visual inspection of the annulus between the encasement and the carrier for one of the pre-1990 transfer lines revealed standing liquid in contact with the carrier pipe. Additionally, a significant build-up of corrosion products on the exterior of the carrier pipe and the interior of the encasement pipe was observed. To assess the extent of condition, borescope inspections were performed in the encasement space of additional transfer lines in the facility to provide a baseline. The inspection revealed that of the lines inspected, 29 had either moisture present or evidence that moisture had been present in the past (e.g., waterline corrosion where the pipe had been exposed to standing water). Additional inspections indicated several instances of pitting corrosion on the interior of the encasement and exterior the carrier transfer lines. An image of the carrier pipe with several pits is presented in Figure 1(a) and the profiled image of the transfer line section along with the pit depths are presented Figure 1(b). As seen in the figure, the deepest pit was 73 mils on the pipe section. These lines were designated as “do-not-use” until further compensatory actions are implemented to return the lines to service.

Shukla, Pavan K. [Savannah River National Laborato↗

DOE OSTI2025

Developing a media formulation to sustain ex vivo chloroplast function

Chloroplasts are critical organelles in plants and algae responsible for accumulating biomass through photosynthetic carbon fixation and cellular maintenance through metabolism in the cell. Chloroplasts are increasingly appreciated for their role in biomanufacturing, as they can produce many useful molecules, and a deeper understanding of chloroplast regulation and function would provide more insight for the biotechnological applications of these organelles. However, traditional genetic approaches to manipulate chloroplasts are slow, and generation of transgenic organisms to study their function can take weeks to months, significantly delaying the pace of research. To develop chloroplasts themselves as a quicker and more defined platform, we isolated chloroplasts from the green algae, Chlamydomonas reinhardtii, and examined their photosynthetic function after extraction. Combined with a metabolic modeling approach using flux-balance analysis, we identified key metabolic reactions essential to chloroplast function and leveraged this information into reagents that can be used in a “chloroplast media” capable of maintaining chloroplast photosynthetic function over time ex vivo compared to buffer alone. We envision this could serve as a model platform to enable more rapid design-build-test-learn cycles to study and improve chloroplast function in combination with genetic modifications and potentially as a starting point for the bottom-up design of a synthetic organelle-containing cell.

Chlamydomonas reinhardtii↗

NASA NTRS2004

Improving Project Management with Simulation and Completion Distribution Functions

Despite the critical importance of project completion timeliness, management practices in place today remain inadequate for addressing the persistent problem of project completion tardiness. A major culprit in late projects is uncertainty, which most, if not all, projects are inherently subject to. This uncertainty resides in the estimates for activity durations, the occurrence of unplanned and unforeseen events, and the availability of critical resources. In response to this problem, this research developed a comprehensive simulation based methodology for conducting quantitative project completion time risk analysis. It is called the Project Assessment by Simulation Technique (PAST). This new tool enables project stakeholders to visualize uncertainty or risk, i.e. the likelihood of their project completing late and the magnitude of the lateness, by providing them with a completion time distribution function of their projects. Discrete event simulation is used within PAST to determine the completion distribution function for the project of interest. The simulation is populated with both deterministic and stochastic elements. The deterministic inputs include planned project activities, precedence requirements, and resource requirements. The stochastic inputs include activity duration growth distributions, probabilities for events that can impact the project, and other dynamic constraints that may be placed upon project activities and milestones. These stochastic inputs are based upon past data from similar projects. The time for an entity to complete the simulation network, subject to both the deterministic and stochastic factors, represents the time to complete the project. Repeating the simulation hundreds or thousands of times allows one to create the project completion distribution function. The Project Assessment by Simulation Technique was demonstrated to be effective for the on-going NASA project to assemble the International Space Station. Approximately $500 million per month is being spent on this project, which is scheduled to complete by 2010. NASA project stakeholders participated in determining and managing completion distribution functions produced from PAST. The first result was that project stakeholders improved project completion risk awareness. Secondly, using PAST, mitigation options were analyzed to improve project completion performance and reduce total project cost.

Cates, Grant R.↗

DOE OSTI2026

Tensor renormalization group approach to critical phenomena via symmetry-twisted partition functions

The locality of field theories strongly constrains the possible behaviors of symmetry-twisted partition functions, and thus they serve as order parameters to detect low-energy realizations of global symmetries, such as spontaneous symmetry breaking (SSB). We demonstrate that the tensor renormalization group (TRG) offers an efficient framework to compute the symmetry-twisted partition functions, which enables us to detect the symmetry-breaking transition and also to study associated critical phenomena. As concrete examples of SSB, we investigate the two-dimensional (2D) classical Ising model and the three-dimensional (3D) classical 𝑂⁡(2) nonlinear sigma model, and we identify their critical points solely from the twisted partition function. By employing the finite-size scaling argument, we find the critical temperature 𝑇 𝑐 = 2.2017⁢(2) with the critical exponent 𝜈 = 0.663⁢(33) for the 3D 𝑂⁡(2) model. In addition, we also study the Berezinskii–Kosterlitz–Thouless (BKT) criticality of the 2D classical 𝑂⁡(2) model by extracting the helicity modulus from the twisted partition functions, and we obtain the BKT transition temperature, 𝑇 BKT = 0.8928⁢(2).

lattice field theory↗

DOE OSTI2022

The Role of Oxygen Transfer in Oxide Heterostructures on Functional Properties

A variety of mechanisms are reported to play critical roles in contributing to the high carrier/electron mobility in oxide/SrTiO 3 (STO) heterostructures. By using La 0.95 Sr 0.05 TiO 3 (LSTO) epitaxially grown on different single crystal substrates (such as STO, GdScO 3 , LaAlO 3 , (LaAlO 3 ) 0.3 (Sr 2 AlTaO 6 ) 0.7 , and CeO 2 buffered STO) as the model systems, the formation of a conducting substrate surface layer (CSSL) on STO substrate is shown at relatively low growth temperature and high oxygen pressure (725 °C, 5 × 10 –4 Torr), which contributes to the enhanced conductivity of the LSTO/STO heterostructures. Different from the conventional oxygen vacancy model, this work reveals that the formation of the CSSL occurs when growing an oxide layer (LSTO in this case) on STO, while neither annealing nor the growth of an Au layer alone at the exact same growth condition generates the CSSL in STO. It demonstrates that the oxide layer actively pulls oxygen from STO substrate at given growth conditions, leading to the formation of the CSSL. Here, the observations emphasize the oxygen transfer across film/substrate interface during the synthesis of oxide heterostructures playing a critical role in functional properties.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Advanced genomics identifies growth effectors for proteotoxic ER stress recovery in Arabidopsis thaliana

Abstract Adverse environmental and pathophysiological situations can overwhelm the biosynthetic capacity of the endoplasmic reticulum (ER), igniting a potentially lethal condition known as ER stress. ER stress hampers growth and triggers a conserved cytoprotective signaling cascade, the unfolded protein response (UPR) for ER homeostasis. As ER stress subsides, growth is resumed. Despite the pivotal role of the UPR in growth restoration, the underlying mechanisms for growth resumption are yet unknown. To discover these, we undertook a genomics approach in the model plant species Arabidopsis thaliana and mined the gene reprogramming roles of the UPR modulators, basic leucine zipper28 (bZIP28) and bZIP60, in ER stress resolution. Through a network modeling and experimental validation, we identified key genes downstream of the UPR bZIP-transcription factors (bZIP-TFs), and demonstrated their functional roles. Our analyses have set up a critical pipeline for functional gene discovery in ER stress resolution with broad applicability across multicellular eukaryotes.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2022

Dynamic, resilient virtual sensing system and shadow controller for cyber-attack neutralization

An industrial asset may have monitoring nodes (e.g., sensor or actuator nodes) that generate current monitoring node values. An abnormality detection and localization computer may receive the series of current monitoring node values and output an indication of at least one abnormal monitoring node that is currently being attacked or experiencing a fault. An actor-critic platform may tune a dynamic, resilient state estimator for a sensor node and output tuning parameters for a controller that improve operation of the industrial asset during the current attack or fault. The actor-critic platform may include, for example, a dynamic, resilient state estimator, an actor model, and a critic model. According to some embodiments, a value function of the critic model is updated for each action of the actor model and each action of the actor model is evaluated by the critic model to update a policy of the actor-critic platform.

Roychowdhury, Subhrajit↗

DOE OSTI2016

SDN Project

The SDN Project completed on time and on budget and successfully accomplished 100% of the scope of work outlined in the original Statement of Project Objective (SOPO). The SDN Project formed an alliance between Ameren Corporation, University of Illinois Urbana- Champaign (UIUC), Pacific Northwest National Laboratories (PNNL), and Schweitzer Engineering Laboratories, Inc. (SEL). The objective of the SDN Project is to address Topic Area of Interest 2: Sustain critical energy delivery functions while responding to a cyber-intrusion under Funding Opportunity Announcement DE-FOA-0000797. The goal of the project is to design and commercially release technology that provides a method to sustain critical energy delivery functions during a cyber intrusion and to do this control system operators need the ability to quickly identify and isolate the affected network areas, and re-route critical information and control flows around. The objective of the SDN Project is to develop a Flow Controller that monitors, configures, and maintains the safe, reliable network traffic flows of all the local area networks (LANs) on a control system in the Energy sector. The SDN team identified the core attributes of a control system and produced an SDN flow controller that has the same core attributes enabling networks to be designed, configured and deployed that maximize the whitelisted, deny-bydefault and purpose built networks. This project researched, developed and commercially released technology that: Enables all field networks be to configured and monitored as if they are a single asset to be protected; Enables greatly improved and even precalculated response actions to reliability and cyber events; Supports pre-configured localized response actions tailored to provide resilience against failures and centralized response to cyber-attacks that improve network reliability and availability; Architecturally enables the right subject matter experts, who are usually the information technology and operational technology engineers, to be the ones centrally administering the technology and responding to events; Simplifies network configuration, improving deterministic Ethernet transport times, and providing instant visualization on where the communication circuits are and how all circuits are impacted when changes (e.g., configuration changes, failures or intrusions) happen, allowing operators to minimize downtime; and Improves the ability to identify deviations in network behavior resulting in detection and analysis of potential cyber intrusions and faster response times Results: This project has forever changed the way critical infrastructure networks are designed, secured, deployed and maintained. The cybersecurity and performance advantages achieved are significant, simply put traditional networking has been obsoleted while the team maintained Ethernet interoperability avoiding any legacy concerns. The team commercially released technology that accomplished all the cybersecurity goals outlined in the SOPO and completed it by executing the project management plan approved in the initial contract. The resulting Energy sector SDN flow controller model number is SEL-5056 and can be freely downloaded from the www.SELinc.com website. This technology not only improves the cybersecurity of control systems but has measured results that it improves the performance and reliability of the control system as well. This means the system owners can confidently apply it to their systems knowing that it will, “first do no harm” but actually improve the system as well. Success of the project is best measured by the sales and deployment of the technology. System owners in industrial, electric, defense, and oil and gas only months after commercial release have approved plans for deployment.

42 ENGINEERING↗

DOE OSTI2019

Room-temperature stability of excitons and transverse-electric polarized deep-ultraviolet luminescence in atomically thin GaN quantum wells

Here, we apply first-principles calculations to study the effects of extreme quantum confinement on the electronic, excitonic, and radiative properties of atomically thin (1–4 atomic monolayers) GaN quantum wells embedded in AlN. We determine the quasiparticle bandgaps, exciton energies and wave functions, radiative lifetimes, and Mott critical densities as a function of well and barrier thickness. Our results show that quantum confinement in GaN monolayers increases the bandgap up to 5.44 eV and the exciton binding energy up to 215 meV, indicating the thermal stability of excitons at room temperature. Exciton radiative lifetimes range from 1 to 3 ns at room temperature, while the Mott critical density for exciton dissociation is approximately 10 13 cm -2 . The luminescence is transverse-electric polarized, which facilitates light extraction from c-plane heterostructures. We also introduce a simple approximate model for calculating the exciton radiative lifetime based on the free-carrier bimolecular radiative recombination coefficient and the exciton radius, which agrees well with our results obtained with the Bethe–Salpeter equation predictions. In conclusion, our results demonstrate that atomically thin GaN quantum wells exhibit stable excitons at room temperature for potential applications in efficient light emitters in the deep ultraviolet as well as room-temperature excitonic devices.

36 MATERIALS SCIENCE↗

NASA NTRS2025

ISS Radiator Face Sheet Anomaly Investigation and Return to Function

Maintaining sufficient heat rejection on the International Space Station (ISS) is critical to the function of the Low-Earth Orbit station. The External Active Thermal Control System (EATCS) rejects the excess heat generated by the US On-Orbit Segment (USOS) modules. The system uses single-phase liquid ammonia to collect the heat and reject it to six radiators (three on the Starboard side, three on the Port side). Each radiator is made up of eight panels. In September 2008, imagery of the Starboard radiators was conducted and showed one of the panels’ face sheets had peeled up from the internal honeycomb core structure. Out of an abundance of caution, the radiator was isolated from the rest of the EATCS and the ammonia was vented to space. Since the radiator was vented, periodic imagery of all radiator panels was taken to monitor any changes in the face sheet and inspect for other radiator anomalies. In January 2025, after years of trending and inspections, the radiator was reintegrated into the system to increase heat rejection capabilities. This paper will document the multi-year investigation that took place to determine root cause and mitigations implemented to reduce risk to the system. A summary of the data since the investigation will show rationale for reintegrating the radiator even with the damaged panel. The goal of the paper is to document the investigation for historical purposes and provide future programs with findings discovered during the investigation.

Aaron Rodriguez↗

NASA NTRS2026

ISS Radiator Face Sheet Anomaly Investigation and Return to Function

Aaron Rodriguez↗

DOE OSTI2019

NECA derivatives exploit the paralog-specific properties of the site 3 side pocket of Grp94, the endoplasmic reticulum Hsp90

The hsp90 chaperones govern the function of essential client proteins critical for normal cell function as well as cancer initiation and progression. Hsp90 activity is driven by ATP, which binds to the N-terminal domain and induces large conformational changes that are required for client maturation. Inhibitors targeting the ATP-binding pocket of the N-terminal domain have anticancer effects, but most bind with similar affinity to cytosolic Hsp90α and Hsp90β, endoplasmic reticulum Grp94, and mitochondrial Trap1, the four cellular hsp90 paralogs. Paralog-specific inhibitors may lead to drugs with fewer side effects. The ATP-binding pockets of the four paralogs are flanked by three side pockets, termed sites 1, 2, and 3, which differ between the paralogs in their accessibility to inhibitors. Previous insights into the principles governing access to sites 1 and 2 have resulted in development of paralog-selective inhibitors targeting these sites, but the rules for selective targeting of site 3 are less clear. Earlier studies identified 5'N-ethylcarboxamido adenosine (NECA) as a Grp94-selective ligand. Here we use NECA and its derivatives to probe the properties of site 3. We found that derivatives that lengthen the 5' moiety of NECA improve selectivity for Grp94 over Hsp90α. Crystal structures reveal that the derivatives extend further into site 3 of Grp94 compared with their parent compound and that selectivity is due to paralog-specific differences in ligand pose and ligand-induced conformational strain in the protein. These studies provide a structural basis for Grp94-selective inhibition using site 3.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2022

The role of the turbulence driving mode for the initial mass function

Turbulence is a critical ingredient for star formation, yet its role for the initial mass function (IMF) is not fully understood. Here we perform magnetohydrodynamical (MHD) simulations of star cluster formation including gravity, turbulence, magnetic fields, stellar heating, and outflow feedback to study the influence of the mode of turbulence driving on IMF. We find that simulations that employ purely compressive turbulence driving (COMP) produce a higher fraction of low-mass stars as compared to simulations that use purely solenoidal driving (SOL). The characteristic (median) mass of the sink particle (protostellar) distribution for COMP is shifted to lower masses by a factor of ∼1.5 compared to SOL. Our simulation IMFs capture the important features of the observed IMF form. We find that turbulence-regulated theories of the IMF match our simulation IMFs reasonably well in the high-mass and low-mass range, but underestimate the number of very low-mass stars, which form towards the later stages of our simulations and stop accreting due to dynamical interactions. Our simulations show that for both COMP and SOL, the multiplicity fraction is an increasing function of the primary mass, although the multiplicity fraction in COMP is higher than that of SOL for any primary mass range. We find that binary mass ratio distribution is independent of the turbulence driving mode. The average specific angular momentum of the sink particles in SOL is a factor of 2 higher than that for COMP. Overall, we conclude that the turbulence driving mode plays a significant role in shaping the IMF.

79 ASTRONOMY AND ASTROPHYSICS↗

NASA NTRSDate not supplied

Overview of Micrometeoroid and Orbital Debris Analysis Process for Mars Sample Return Earth Entry System

Introduction: Micrometeoroid and orbital debris (MMOD) risk analyses for the Mars Sample Return (MSR) Earth Entry System (EES) have been significantly more rigorous than previously flown missions because of its categorization as a Class V restricted return mission. This means the returned samples present significant concern for biogenic contamination. These analyses seek to determine if a micrometeoroid or orbital debris strike would result in loss of containment assurance and are summarized in the flowchart in Fig. 1. Methodology: The mission is considered in two MMOD phases: a pre-release phase where the EES is protected by a Micrometeoroid Protection System (MMPS) and a post-release phase called “free-flight” where the EES is exposed directly to the MMOD environment. These phases correspond to interplanetary cruise and imminent re-entry, respectively. To inform the MMPS design, a 30-shot high velocity impact testing (HVIT) series on candidate configurations at NASA White Sands Test Facility was completed in the summer of 2022. Sample post-shot images are shown in Fig 2 [1]. These data are used to baseline the MMPS design and to tune the hydrocode simulations. ALE3D, CTH, and SPHC are the hydrocodes that simulate physics of high-speed impacts [2]. Results generated with these populate a penetration depth versus energy space beyond the testable velocity regime of HVIT (~7 km/s). The penetration depth versus energy space data are used to define a critical projectile diameter function called a Ballistic Limit Equation (BLE), where the projectile “criticality” is determined by zone dependent failure criteria defined a-priori [3]. For example, the nose of the heatshield has a failure criterion of 50% TPS penetration, assigned because the landing loads are concentrated on that region and no substructure damage is permitted. The BLEs for each vehicle material zone are input into the BUMPER 3 code, along with the vehicle surface mesh and the corresponding space environment model, to calculate a probability of penetration or number of penetrations. The environment models, MEM3 for MM and ORDEM 3.2 for OD, simulate the meteoroid environment from 0.2 to 2 au based on the Grün flux equation, and the debris environment up to 40,000 km altitude from Earth surface, respectively [4,5]. Presentation Focus: The presentation or poster will present the results to-date focusing on the full risk analysis process flow seen in Fig. 1. Details on the derivation of the failure criteria will be discussed, along with HVIT results and how these influenced the MMPS configuration baseline decision. Further, results of hydrocode simulations will be presented and the tuning to HVIT outputs will be described. Finally, the strategies that direct the BLE formulation will be reviewed, specifically, for the EES elements that are most exposed to the MMOD environment.

mmod↗

DOE OSTI2014

Predicting critical temperatures of iron(II) spin crossover materials: Density functional theory plus U approach

A first-principles study of critical temperatures (T{sub c}) of spin crossover (SCO) materials requires accurate description of the strongly correlated 3d electrons as well as much computational effort. This task is still a challenge for the widely used local density or generalized gradient approximations (LDA/GGA) and hybrid functionals. One remedy, termed density functional theory plus U (DFT+U) approach, introduces a Hubbard U term to deal with the localized electrons at marginal computational cost, while treats the delocalized electrons with LDA/GGA. Here, we employ the DFT+U approach to investigate the T{sub c} of a pair of iron(II) SCO molecular crystals (α and β phase), where identical constituent molecules are packed in different ways. We first calculate the adiabatic high spin-low spin energy splitting ΔE{sub HL} and molecular vibrational frequencies in both spin states, then obtain the temperature dependent enthalpy and entropy changes (ΔH and ΔS), and finally extract T{sub c} by exploiting the ΔH/T − T and ΔS − T relationships. The results are in agreement with experiment. Analysis of geometries and electronic structures shows that the local ligand field in the α phase is slightly weakened by the H-bondings involving the ligand atoms and the specific crystal packing style. We find that this effect is largely responsible for the difference in T{sub c} of the two phases. This study shows the applicability of the DFT+U approach for predicting T{sub c} of SCO materials, and provides a clear insight into the subtle influence of the crystal packing effects on SCO behavior.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗