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617 records · Page 35

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DOE OSTI2026

Solubility-limited depolymerization kinetics in the glycolysis of carbonyl-containing polymers

Chemical recycling of condensation polymers is often rationalized on the basis of the intrinsic reactivity of ester and carbonate functional groups. However, under heterogeneous conditions relevant to plastic waste processing and environmental degradation, bulk depolymerization rates often diverge from trends predicted by homogeneous chemistry. Here, we investigate how polymer–solvent compatibility, catalyst strength, and phase behavior govern the heterogeneous glycolysis of carbonyl-containing polymers. Using poly(ethylene terephthalate) (PET), glycol-modified PET (PETG), and bisphenol-A polycarbonate (PC) as model systems, we examine depolymerization kinetics at 180 °C with ethylene glycol and bisphenol A as diols under both amphoteric organosalt (TBD : MSA) and strong base (TBD) catalysis. Despite substantial differences in crystallinity and glycol uptake, PET and PETG depolymerize at comparable rates under organosalt catalysis, while PC depolymerizes significantly more slowly under identical conditions. Time-resolved molecular weight analysis and thermal characterization demonstrate that these rate differences do not arise from crystallinity, swelling, or inherent carbonyl reactivity, but instead reflect solubility-limited kinetics that constrain the transition from heterogeneous to homogeneous reaction regimes. When polymer solubility is low, depolymerization remains heterogeneous and slow; when solubility is enhanced—either through increased polymer–diol compatibility or stronger base catalysis—rapid homogeneous depolymerization is observed, reversing apparent reactivity trends. These results establish solubility and phase behavior as primary determinants of depolymerization kinetics in heterogeneous polymer recycling systems. By demonstrating how catalyst selection and solvent compatibility can expose or overcome solubility limitations, this work provides mechanistic insight to design more energy-efficient and selective chemical recycling processes. More broadly, these findings suggest that polymers with limited solvent or water compatibility may resist chemical degradation in the environment, favoring fragmentation and persistence as micro- and nanoplastics. Understanding solubility-controlled depolymerization offers a pathway toward more sustainable polymer design and end-of-life chemical recovery.

Watson-Sanders, Shelby [Department of Chemistry, U↗

DOE OSTI2026

Multireference Embedding and Fragmentation Methods for Classical and Quantum Computers: From Model Systems to Realistic Applications

One of the primary challenges in quantum chemistry is the accurate modeling of strong electron correlation. While multireference methods effectively capture such correlation, their steep scaling with system size prohibits their application to large molecules and extended materials. Quantum embedding offers a promising solution by partitioning complex systems into manageable subsystems. In this Review, we highlight recent advances in multireference density matrix embedding and localized active space self-consistent field approaches for complex molecules and extended materials. We discuss both classical implementations and the emerging potential of these methods on quantum computers. Here, by extending classical embedding concepts to the quantum landscape, these algorithms have the potential to expand the reach of multireference methods in quantum chemistry and materials.

Algorithms↗

DOE OSTI2020

Development and demonstration of a methodology to evaluate high burnup fuel susceptibility to pulverization under a loss of coolant transient

For economic reasons, the US nuclear industry is renewing efforts to build a technical basis to extend rod average burnup limits above the current regulatory burnup limit of 62 GWd/MTU. The primary driver is to increase pressurized water reactor cycle lengths to 24 months, reducing the number of fresh fuel assemblies and core design constraints, thereby making core energy utilization more efficient. However, fuel pellet fragmentation and pulverization, termed high burnup fuel fragmentation (HBFF), has been observed in the high burnup (>90 GWd/MTU) Halden loss-of-coolant-accident (LOCA) integral test series. The issue gained attention when fuel fragmentation and pulverization were also observed closer to the current US regulatory limit during the US Nuclear Regulatory Commission (NRC) sponsored out-of-core integral test at Studsvik Nuclear in early 2011. This led to NRC concerns with potential changes to fuel and core designs relative to fuel pellet pulverization. In a letter to the NRC Commissioners, the staff specifically identified a need to “…define the boundary of safe operation for key fuel design and operating parameters,” stating that “the staff is challenged to evaluate the acceptability of future fuel design advancements and fuel utilization changes.” As such, it can be concluded that HBFF and potential dispersal into the reactor coolant system introduces additional complications in light-water reactor (LWR) fuel safety evaluations. However, it is not clear how much fuel will be susceptible to HBFF; nor has there been a methodology developed to evaluate fuel susceptibility to HBFF. To that end, this paper proposes an analysis methodology to assess fuel susceptibility to HBFF during LOCA scenarios. The work presented here uses the BISON fuel performance code to evaluate a representative pressurized water reactor fuel rod exposed to a rod average burnup of 75 GWd/MTU. Sensitivity studies investigated the impact of the peak cladding temperature, transient fission gas released, and pre-transient fission gas release on cladding ballooning and burst timing. Subsequently, a methodology to assess fuel susceptibility to HBFF will be developed based on experimental data published in the open literature. The methodology will then be demonstrated by calculating the mass of fuel susceptibility to HBFF. The BISON results conclude that increasing peak cladding temperature drastically decreased time to failure, and decreased balloon size both of which have been confirmed experimentally. Additionally, the effect of pre-transient and transient fission gas release affected cladding balloon size and burst timing. Finally, fuel susceptibility to HBFF significantly decreased as a function of peak cladding temperature.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2021

Ab Initio Direct Dynamics

The reactivity and dynamics of molecular systems can be explored computationally by classical trajectory calculations. The traditional approach involves fitting a functional form of a potential energy surface (PES) to the energies from a large number of electronic structure calculations and then integrating numerous trajectories on this fitted PES to model the molecular dynamics. The ever-decreasing cost of computing and continuing advances in computational chemistry software have made it possible to use electronic structure calculations directly in molecular dynamics simulations without first having to construct a fitted PES. In this “on-the-fly” approach, every time the energy and its derivatives are needed for the integration of the equations of motion, they are obtained directly from quantum chemical calculations. This approach started to become practical in the mid-1990s as a result of increased availability of inexpensive computer resources and improved computational chemistry software. The application of direct dynamics calculations has grown rapidly over the last 25 years and would require a lengthy review article. The present Account is limited to some of our contributions to methods development and various applications. To improve the efficiency of direct dynamics calculations, we developed a Hessian-based predictor-corrector algorithm for integrating classical trajectories. Hessian updating made this even more efficient. Furthermore, this approach was also used to improve algorithms for following the steepest descent reaction paths. For larger molecular systems, we developed an extended Lagrangian approach in which the electronic structure is propagated along with the molecular structure. Strong field chemistry is a rapidly growing area, and to improve the accuracy of molecular dynamics in intense laser fields, we included the time-varying electric field in a novel predictor-corrector trajectory integration algorithm. Since intense laser fields can excite and ionize molecules, we extended our studies to include electron dynamics. Specifically, we developed code for time-dependent configuration interaction electron dynamics to simulate strong field ionization by intense laser pulses. Our initial application of ab initio direct dynamics in 1994 was to CH 2 O → H 2 + CO; the calculated vibrational distributions in the products were in very good agreement with experiment. In the intervening years, we have used direct dynamics to explore energy partitioning in various dissociation reactions, unimolecular dissociations yielding three fragments, reactions with branching after the transition state, nonstatistical dynamics of chemically activated molecules, dynamics of molecular fragmentation by intense infrared laser pulses, selective activation of specific dissociation channels by aligned intense infrared laser fields, angular dependence of strong field ionization, and simulation of sequential double ionization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Urbanization and edge effects interact to drive mutualism breakdown and the rise of unstable pathogenic communities in forest soil

Temperate forests are threatened by urbanization and fragmentation, with over 20% (118,300 km 2 ) of U.S. forest land projected to be subsumed by urban land development. We leveraged a unique, well-characterized urban-to-rural and forest edge-to-interior gradient to identify the combined impact of these two land use changes—urbanization and forest edge creation—on the soil microbial community in native remnant forests. We found evidence of mutualism breakdown between trees and their fungal root mutualists [ectomycorrhizal (ECM) fungi] with urbanization, where ECM fungi colonized fewer tree roots and had less connectivity in soil microbiome networks in urban forests compared to rural forests. However, urbanization did not reduce the relative abundance of ECM fungi in forest soils; instead, forest edges alone led to strong reductions in ECM fungal abundance. At forest edges, ECM fungi were replaced by plant and animal pathogens, as well as copiotrophic, xenobiotic-degrading, and nitrogen-cycling bacteria, including nitrifiers and denitrifiers. Urbanization and forest edges interacted to generate new “suites” of microbes, with urban interior forests harboring highly homogenized microbiomes, while edge forest microbiomes were more heterogeneous and less stable, showing increased vulnerability to low soil moisture. When scaled to the regional level, we found that forest soils are projected to harbor high abundances of fungal pathogens and denitrifying bacteria, even in rural areas, due to the widespread existence of forest edges. Our results highlight the potential for soil microbiome dysfunction—including increased greenhouse gas production—in temperate forest regions that are subsumed by urban expansion, both now and in the future.

54 ENVIRONMENTAL SCIENCES↗