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At least 307 records · Page 17
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Electron transfer in a crystalline cytochrome with four hemes

Diffusion of electrons over distances on the order of 100 μm has been observed in crystals of a small tetraheme cytochrome (STC) from Shewanella oneidensis [J. Huang et al . J. Am. Chem. Soc. 142, 10459–10467 (2020)]. Electron transfer between hemes in adjacent subunits of the crystal is slower and more strongly dependent on temperature than had been expected based on semiclassical electron-transfer theory. Here, in this work, we explore explanations for these findings by molecular-dynamics simulations of crystalline and monomeric STC. New procedures are developed for including time-dependent quantum mechanical energy differences in the gap between the energies of the reactant and product states and for evaluating fluctuations of the electronic-interaction matrix element that couples the two hemes. Rate constants for electron transfer are calculated from the time- and temperature-dependent energy gaps, coupling factors, and Franck–Condon-weighted densities of states using an expression with no freely adjustable parameters. Back reactions are considered, as are the effects of various protonation states of the carboxyl groups on the heme side chains. Interactions with water are found to dominate the fluctuations of the energy gap between the reactant and product states. The calculated rate constant for electron transfer from heme IV to heme Ib in a neighboring subunit at 300 K agrees well with the measured value. However, the calculated activation energy of the reaction in the crystal is considerably smaller than observed. We suggest two possible explanations for this discrepancy. The calculated rate constant for transfer from heme I to II within the same subunit of the crystal is about one-third that for monomeric STC in solution.

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

Dynamics of Hydrophobic Core Phenylalanine Residues Probed by Solid-State Deuteron NMR

We conducted a detailed investigation of the dynamics of two phenylalanine side chains in the hydrophobic core of the villin headpiece subdomain protein (HP36) in the hydrated powder state over the 298–80 K temperature range. We utilized static deuteron NMR measurements of longitudinal relaxation and line shapes supplemented with computational modeling. The temperature dependence of the relaxation times reveals the presence of two main mechanisms that can be attributed to the ring-flips, dominating at high temperatures, and small-angle fluctuations, dominating at low temperatures. The relaxation is non- exponential at all temperatures with the extent of non-exponentiality increasing from higher to lower temperatures. This behavior suggests a distribution of conformers with unique values of activation energies. The central values of the activation energies for the ring-flipping motions are among the smallest reported for aromatic residues in peptides and proteins and point to a very mobile hydrophobic core. The analysis of the widths of the distributions, in combination with the earlier results on the dynamics of flanking methyl groups (Vugmeyster et al., J. Phys. Chem. 2013, 117, 6129–6137), suggests that the hydrophobic core undergoes concerted fluctuations. There is a pronounced effect of dehydration on the ring-flipping motions, which shifts the distribution toward more rigid conformers. The cross-over temperature between the regions of dominance of the small-angle fluctuations and ring-flips shifts from 195 K in the hydrated protein to 278 K in the dry one. This result points to the role of solvent in the onset of the concerted fluctuations of the core and highlights aromatic residues as markers of the protein dynamical transitions.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2012

Insight from molecular modelling: does the polymer side chain length matter for transport properties of perfluorosulfonic acid membranes?

We present a detailed analysis of the nanostructure of short side chain (SSC) perfluorosulfonic acid membrane and its effect on H{sub 2}O network percolation, H{sub 3}O{sup +} and H{sub 2}O diffusion, and mean residence times of H{sub 3}O{sup +} and H{sub 2}O near SO{sub 3}{sup -} groups based on molecular dynamics simulations. We studied a range of hydration levels ({lambda}) at temperatures of 300 and 360 K, and compare the results to our previous findings in the benchmark Nafion membrane at 300 K. The water channel diameter is about 20% larger in Nafion, while the extent of SO3- clustering is more in SSC membrane. The calculated channel diameter is in excellent agreement with the recently proposed cylindrical water channel model of these membranes. The H{sub 2}O network percolation occurs at comparable hydration levels, and the diffusion coefficients of H{sub 2}O and H{sub 3}O{sup +} are similar in SSC and Nafion membranes. Raising the temperature of the SSC membrane from 300 to 360 K provides a much bigger increase in proton vehicular diffusion coefficient (by a factor of about 4) than changing the side chain length. H3O+ ions are found to exchange more frequently with SO{sub 3}{sup -} partners at the higher temperature. Our key findings are that (a) the hydrophobic-hydrophilic separation in the two membranes is surprisingly similar; (b) at all hydration levels studied, the longer side chain of Nafion is bent and is effectively equivalent to a short side chain in terms of extension into the water domain; and (c) proton transport along the centre of the channel is improbable and vehicular proton transport occurs between SO{sub 3}{sup -} groups. The simulations are validated by good agreement with corresponding experimental values for the simulated membrane density and diffusion coefficients of H{sub 2}O.

30 DIRECT ENERGY CONVERSION↗
NASA NTRS1992

Assured crew return vehicle post landing configuration design and test

The 1991-1992 senior Mechanical and Aerospace Engineering Design class continued work on the post landing configurations for the Assured Crew Return Vehicle (ACRV) and the Emergency Egress Couch (EEC). The ACRV will be permanently docked to Space Station Freedom, fulfilling NASA's commitment of Assured Crew Return Capability in the event of an accident or illness aboard Space Station Freedom. The EEC provides medical support and a transportation surface for an incapacitated crew member. The objective of the projects was to give the ACRV Project Office data to feed into their feasibility studies. Four design teams were given the task of developing models with dynamically and geometrically scaled characteristics. Groups one and two combined effort to design a one-fifth scale model of the Apollo Command Module derivative, an on-board flotation system, and a lift attachment point system. This model was designed to test the feasibility of a rigid flotation and stabilization system and to determine the dynamics associated with lifting the vehicle during retrieval. However, due to priorities, it was not built. Group three designed a one-fifth scale model of the Johnson Space Center (JSC) benchmark configuration, the Station Crew Return Alternative Module (SCRAM) with a lift attachment point system. This model helped to determine the flotation and lifting characteristics of the SCRAM configuration. Group four designed a full scale EEC with changeable geometric and dynamic characteristics. This model provided data on the geometric characteristics of the EEC and on the placement of the CG and moment of inertia. It also gave the helicopter rescue personnel direct input to the feasibility study.

Anderson, Loren A.↗
DOE OSTI2015

RESONANCES, CHAOS, AND SHORT-TERM INTERACTIONS AMONG THE INNER URANIAN SATELLITES

The Portia group of Uranian satellites, representing 9 of the planet’s 13 tiny innermost moons, form a densely packed dynamical system. Hubble Space Telescope observations indicate that their orbits have changed significantly over two decades, and long-term numerical integrations show that their orbits are unstable over millions of years. To investigate the dynamical interactions of the Portia group satellites on the decade timescale over which orbital changes have been observed, we have performed a suite of 100–1000 yr N-body numerical integrations for a range of assumed satellite masses, which are at present not tightly constrained by observations. As first noted by Dawson et al. and recently investigated independently by Quillen and (Robert) French, the moons are configured in chains of interlinked first- and second-order eccentric resonances that contribute to chaotic behavior. We explore in detail several of the strongest of these interlinked resonances. The first such chain is a quintet of orbital resonances: Bianca is near a resonance with Cressida, which is itself near a resonance with Desdemona. Desdemona, in turn, is near a resonance with Portia, which is itself near a resonance with Juliet. The five participating resonances are: Cressida and Bianca (16:15), Desdemona and Cressida (47:46), Portia and Desdemona (13:12), and Portia and Juliet (51:49). A second such chain is a set of two interlinked resonances: Cupid and Belinda (58:57) and Belinda and Perdita (44:43). We also report the new identification of a companion set of second-order inclination-type resonances (Cressida and Bianca (32:30), Desdemona and Cressida (94:92), Portia and Desdemona (26:24), Portia and Juliet (51:49), Cupid and Belinda (116:114), and Belinda and Perdita (88:86)), some of which result in quite strongly coupled variations in the inclinations of the interacting satellites. Using a robust formulation of orbital elements that accounts for the oblateness of Uranus, we probe the dynamical interactions among the moons in the time and frequency domains, and also in phase space, using numerical integrations of subsets of the inner moons, for a range of assumed masses. Several of the satellites are near mean-motion resonance with more than one neighbor, and undergo orbital variations at two nearly equal resonant frequencies. Such configurations of two interlinked resonances can result in chaotic behavior, associated with the transition of one resonant argument from circulation to libration. We demonstrate that, even on the short timescales investigated here, the dynamical interactions, onset of chaos, and associated Lyapunov times are highly sensitive to the masses of the interacting satellites.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS2014

ldentifying Episodes of Earth Science Phenomena Using a Big-Data Technology

A significant portion of Earth Science investigations is phenomenon- (or event-) based, such as the studies of Rossby waves, volcano eruptions, tsunamis, mesoscale convective systems, and tropical cyclones. However, except for a few high-impact phenomena, e.g. tropical cyclones, comprehensive records are absent for the occurrences or events of these phenomena. Phenomenon-based studies therefore often focus on a few prominent cases while the lesser ones are overlooked. Without an automated means to gather the events, comprehensive investigation of a phenomenon is at least time-consuming if not impossible. We have constructed a prototype Automated Event Service (AES) system that is used to methodically mine custom-defined events in the reanalysis data sets of atmospheric general circulation models. Our AES will enable researchers to specify their custom, numeric event criteria using a user-friendly web interface to search the reanalysis data sets. Moreover, we have included a social component to enable dynamic formation of collaboration groups for researchers to cooperate on event definitions of common interest and for the analysis of these events. An Earth Science event (ES event) is defined here as an episode of an Earth Science phenomenon (ES phenomenon). A cumulus cloud, a thunderstorm shower, a rogue wave, a tornado, an earthquake, a tsunami, a hurricane, or an El Nino, is each an episode of a named ES phenomenon, and, from the small and insignificant to the large and potent, all are examples of ES events. An ES event has a duration (often finite) and an associated geo-location as a function of time; it's therefore an entity embedded in four-dimensional (4D) spatiotemporal space. Earth Science phenomena with the potential to cause massive economic disruption or loss of life often rivet the attention of researchers. But, broader scientific curiosity also drives the study of phenomena that pose no immediate danger, such as land/sea breezes. Due to Earth System's intricate dynamics, we are continuously discovering novel ES phenomena. We generally gain understanding of a given phenomenon by observing and studying individual events. This process usually begins by identifying the occurrences of these events. Once representative events are identified or found, we must locate associated observed or simulated data prior to commencing analysis and concerted studies of the phenomenon. Knowledge concerning the phenomenon can accumulate only after analysis has started. However, as mentioned previously, comprehensive records only exist for a very limited set of high-impact phenomena; aside from these, finding events and locating associated data currently may take a prohibitive amount of time and effort on the part of an individual investigator. The reason for the lack of comprehensive records for most of the ES phenomena is mainly due to the perception that they do not pose immediate and/or severe threat to life and property. Thus they are not consistently tracked, monitored, and catalogued. Many phenomena even lack precise and/or commonly accepted criteria for definitions. Moreover, various Earth Science observations and data have accumulated to a previously unfathomable volume; NASA Earth Observing System Data Information System (EOSDIS) alone archives several petabytes (PB) of satellite remote sensing data, which are steadily increasing. All of these factors contribute to the difficulty of methodically identifying events corresponding to a given phenomenon and significantly impede systematic investigations. We have not only envisioned AES as an environment for identifying customdefined events but also aspired for it to be an interactive environment with quick turnaround time for revisions of query criteria and results, as well as a collaborative environment where geographically distributed experts may work together on the same phenomena. A Big Data technology is thus required for the realization of such a system. In the following, we first introduce the technology selected for AES in the next section. We then demonstrate the utility of AES using a use case, Blizzard, before we conclude.

Kuo, Kwo-Sen↗
DOE OSTI2025

Oscillate and renormalize: Fast phonons reshape the Kondo effect in flat-band systems

Here, we examine the interplay between electron correlations and phonons in an Anderson-Holstein impurity model with an Einstein phonon. When the phonons are slow compared to charge fluctuations (frequency 𝜔 0 ≪ 𝑈/2, the onsite Coulomb scale 𝑈/2), we demonstrate analytically that the expected phonon-mediated reduction of interactions is completely suppressed, even in the strong-coupling regime. This suppression arises from the oscillator's inability to respond to rapid charge fluctuations, manifested as a compensation effect between the polaronic cloud and the excited-state phonons associated with valence fluctuations. We identify a frozen mixed valence phase, above a threshold dimensionless electron-phonon coupling 𝛼* when the phonons are slow, where the static phonon cloud locks the impurity into specific valence configurations, potentially explaining the puzzling coexistence of mixed valence behavior and insulating properties in materials like rust. Conversely, when the phonon is fast (𝜔 0 ≳ 𝑈/2), the system exhibits conventional polaronic behavior with renormalized onsite interactions effectively 𝑈 eff due to phonon-mediated attraction, with additional satellite features in the local spectral function due to phonon excitations. Using numerical renormalization group calculations, a fully dynamic renormalization technique, we confirm these behaviors in both regimes. These findings have important implications for strongly correlated systems where phonon energy scales may be comparable to the Coulomb scale, such as in twisted bilayer graphene, necessitating careful consideration of interaction renormalizations in theoretical models.

Anderson impurity model↗
DOE OSTI2023

On the role of methyl groups in the molecular architectures of mesophase pitches

The role of methyl groups on the liquid–crystal structure of mesophase pitches was investigated by combining experimental characterizations and atomic-scale computational modeling, using three pitches synthesized from different precursors. Of the three pitches, C-9 alkyl benzene and naphthalene-based pitches have 13 and 7 methyl groups per average polyaromatic hydrocarbon, respectively. By contrast, mesophase produced from a coal-tar pitch has about one methyl group. The coal tar–based mesophase pitch is hydrogen deficient or more aromatic compared with C-9 alkyl benzene- and naphthalene-based pitches. Additionally, X-ray diffraction data showed that average coherent domain sizes of C-9 alkyl benzene (3.7 nm) and naphthalene-based (3.6 nm) pitches with more methyl groups are larger than that of coal tar–based mesophase (2.4 nm). Based on the identified features, the influence of the methyl group on the layering structures was investigated via molecular dynamics simulations. The results revealed that methyl groups are critical in mesophase layering in C-9 alkyl benzene- and naphthalene-based pitches, by reducing CH-π interaction. However, similar alignment could be achieved without the same degree of methyl substitutions for the coal tar-based pitch because of stronger π-π interaction than the other precursors. The insights from this study contribute to our understanding of the formation of conventional mesophase pitch and have implications for the processing of coal-derived materials. In conclusion, this knowledge is vital to produce valuable products like carbon fiber and graphite from pitches.

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

PAIRS AND GROUPS OF GENETICALLY RELATED LONG-PERIOD COMETS AND PROPOSED IDENTITY OF THE MYSTERIOUS LICK OBJECT OF 1921

We present the history of investigation of the dynamical properties of pairs and groups of genetically related long-period comets (other than the Kreutz sungrazing system). Members of a comet pair or group move in nearly identical orbits, and their origin as fragments of a common parent comet is unquestionable. The only variable is the time of perihelion passage, which differs considerably from member to member owing primarily to an orbital-momentum increment acquired during breakup. Meter-per-second separation velocities account for gaps of years or tens of years, thanks to the orbital periods of many millennia. The physical properties of individual members may not at all be alike, as illustrated by the trio of C/1988 A1, C/1996 Q1, and C/2015 F3. We exploit orbital similarity to examine whether the enigmatic and as-yet-unidentified object discovered from the Lick Observatory near the Sun at sunset on 1921 August 7 happened to be a member of such a pair and to track down the long-period comet to which it might be genetically related. Our search shows that the Lick object, which could not be a Kreutz sungrazer, was likely a companion to comet C/1847 C1 (Hind), whose perihelion distance was ∼9 R {sub ⊙} and true orbital period was approximately 8300 yr. The gap of 74.4 yr between their perihelion times is consistent with a separation velocity of ∼1 m s{sup −1} which sets the fragments apart following the parent's breakup in a general proximity of perihelion during the previous return to the Sun in the seventh millennium BCE.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS1992

Assured crew return vehicle post landing configuration design and test

The 1991-1992 senior Mechanical and Aerospace Engineering Design class continued work on the post landing configurations for the Assured Crew Return Vehicle (ACRV) and the Emergency Egress Couch (EEC). The ACRV will be permanently docked to Space Station Freedom fulfilling NASA's commitment of Assured Crew Return Capability in the event of an accident or illness aboard Space Station Freedom. The EEC provides medical support and a transportation surface for an incapacitated crew member. The objective of the projects was to give the ACRV Project Office data to feed into their feasibility studies. Four design teams were given the task of developing models with dynamically and geometrically scaled characteristics. Groups one and two combined efforts to design a one-fifth scale model for the Apollo Command Module derivative, an on-board flotation system, and a lift attachment point system. This model was designed to test the feasibility of a rigid flotation and stabilization system and to determine the dynamics associated with lifting the vehicle during retrieval. However, due to priorities, it was not built. Group three designed a one-fifth scale model of the Johnson Space Center (JSC) benchmark configuration, the Station Crew Return Alternative Module (SCRAM) with a lift attachment point system. This model helped to determine the flotation and lifting characteristics of the SCRAM configuration. Group four designed a full scale EEC with changeable geometric and geometric and dynamic characteristics. This model provided data on the geometric characteristics of the EEC and on the placement of the CG and moment of inertia. It also gave the helicopter rescue personnel direct input to the feasibility study. Section 1 describes in detail the design of a one-fifth scale model of the Apollo Command Module Derivative (ACMD) ACRV. The objective of the ACMD Configuration Model Team was to use geometric and dynamic constraints to design a one-fifth scale working model of the Apollo Command Module Derivative (ACMD) configuration with a Lift Attachment Point (LAP) System. This model was required to incorporate a rigidly mounted flotation system and the egress system designed the previous academic year. The LAP system was to be used to determine the dynamic effects of locating the lifting points at different locations on the vehicle. The team was then to build and test the model; however, due to priorities, this did not occur. To better simulate the ACMD after a water landing, the nose cone section was removed and the deck area exposed. The areas researched during the design process were construction, center of gravity and moment of inertia, and lift attachment points.

Source record↗
NASA NTRSDate not supplied

Autonomous Control for Arbitrary Thruster Configurations and Mass Properties in Special Euclidean Group SE(3)

Most current methods for determining maneuvers and thrust firing sequences depend on explicit and predetermined commands generated by a combination of on-board systems and ground-based human-in-the-loop methods. For spacecraft and space structures with changing mass properties and thruster configurations, such as the Deep Space Gateway as it changes configurations throughout its lifetime, determining these commands can be time-consuming and computationally intensive. However, recent work within the Lie group SE(3) has offered ways of autonomously determining the location, power, precision, and capabilities of thrusters in any arbitrary position. Furthermore, a method for determining thruster firing sequences based on an arbitrary control input (both translational and rotational in a coupled, 6-element vector) and arbitrary thruster configurations has also recently been developed. When combining these methods, any spacecraft with any mass properties and thruster configurations can be understood in terms of controllability limits and thruster firing sequences can be generated quickly and with low computational load, thus extending the autonomous capabilities of deep space missions. In this work, this method is presented and explored in terms of convergence time to the desired pose. The capabilities of this method are also examined in the case of the Deep Space Gateway both in fully controllable configurations and uncontrollable configurations.

SE(3)↗
DOE OSTI2022

Local Group timing argument and virial theorem mass estimators from cosmological simulations

ABSTRACT We identify Local Group (LG) analogues in the IllustrisTNG cosmological simulation, and use these to study two-mass estimators for the LG: One based on the timing argument (TA) and one based on the virial theorem (VT). Including updated measurements of the Milky Way-M31 tangential velocity and the cosmological constant, we show that the TA mass estimator slightly overestimates the true median LG-mass, though the ratio of the TA to the true mass is consistent at the approximate 90 per cent c.l.. These are in broad agreement with previous results using dark matter-only simulations. We show that the VT estimator better estimates the true LG-mass, though there is a larger scatter in the virial mass to true mass ratio relative to the corresponding ratio for the TA. We attribute the broader scatter in the VT estimator to several factors, including the predominantly radial orbits for LG satellite galaxies, which differs from the VT assumption of isotropic orbits. With the systematic uncertainties we derive, the updated measurements of the LG mass at 90 per cent c.l. are $4.75_{-2.41}^{+2.22} \times 10^{12}$ M⊙ from the TA and $2.0_{-1.5}^{+2.1} \times 10^{12}$ M⊙ from the VT. We consider the LMC’s effect on the TA and VT LG mass estimates, and do not find exact LMC–MW–M31 analogues in the Illustris simulations. However, in LG simulations with satellite companions as massive as the LMC, we find that the effect on the TA and VT estimators is small, though we need further studies on a larger sample of LMC–MW–M31 systems to confirm these results.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2019

Fine‐root traits are linked to species dynamics in a successional plant community

Abstract Despite the importance of fine roots for the acquisition of soil resources such as nitrogen and water, the study of linkages between traits and both population and community dynamics remains focused on aboveground traits. We address this gap by investigating associations between belowground traits and metrics of species dynamics. Our analysis included 85 species from a long‐term data set on the transition from old field to forest in eastern North America (the Buell‐Small Succession Study) and the new Fine‐Root Ecology Database. Given the prominent roles of life form (woody vs. non‐woody) and species origin (native vs. exotic) in defining functional relationships, we also assessed whether traits or their relationships with species dynamics differed for these groups. Species that reached their peak abundance early in succession had fine‐root traits corresponding to resource acquisitive strategies (i.e., they were thinner, less dense, and had higher nitrogen concentrations) while species that peaked progressively later had increasingly conservative strategies. In addition to having more acquisitive root traits than native species, exotics diverged from the above successional trend, having consistently thinner fine roots regardless of the community context. Species with more acquisitive fine‐root morphologies typically had faster rates of abundance increase and achieved their maximal rates in fewer years. Decreasing soil nutrient availability and increasing belowground competition may become increasingly strong filters in successional communities, acting on root traits to promote a transition from acquisitive to conservative foraging. However, disturbances that increase light and soil resource availability at local scales may allow acquisitive species, especially invasive exotics, to continue colonizing late into the community transition to forest.

Caplan, Joshua S.↗
DOE OSTI2023

QMMM 2023: A program for combined quantum mechanical and molecular mechanical modeling and simulations

Combined quantum mechanical and molecular mechanical (QM/MM) methods play an important role in multiscale modeling and simulations. QMMM 2023 is a general-purpose program for single-point calculations, geometry optimizations, transition-state optimizations, and molecular dynamics (MD) at the QM/MM level. It calls a QM package and an MM package to perform the required single-level calculations and combines them into a QM/MM energy by a variety of schemes. QMMM 2023 supports GAMESS-US, Gaussian, and ORCA as QM packages and Tinker as the MM package. Four types of treatments are available for embedding the QM subsystem in the MM environment: mechanical embedding with gas-phase calculations of the QM region, electronic embedding that allows polarization of the QM region by the MM environment, polarizable embedding for mutual polarization of the QM and MM regions, and flexible embedding for both mutual polarization and partial charge transfer between the QM and MM regions. Boundaries between QM and MM regions that pass through covalent bonds can be treated by several methods, including the redistributed charge (RC) scheme, redistributed charge and dipole (RCD) scheme, balanced-RC scheme, balanced-RCD scheme, screened charge scheme that takes account of charge penetration effects, and smeared charge scheme that delocalizes the MM charges near the QM–MM boundary. Geometry optimization can be done using the optimizer implemented in QMMM 2023 or the Berny optimizer in Gaussian through external calls to Gaussian. Molecular dynamics simulations can be performed at the pure-MM level, pure-QM level, fixed-partitioning QM/MM level, and adaptive-partitioning QM/MM level. As a result, the adaptive-partitioning treatments permit on-the-fly relocation of the QM–MM boundary by dynamically reclassifying atoms or groups into the QM or MM subsystems.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2019

Heat capacity and thermodynamic functions of crystalline forms of the metal-organic framework zinc 2-methylimidazolate, Zn(MeIm) 2

Zeolitic imidazolate frameworks (ZIFs) are comprised of metal atoms connected with imidazole-like linkers, and these frameworks have potential for applications in molecular sieving, gas sequestration, and catalysis. Furthermore, these materials form true polymorphs with the same chemical composition but different topologies. In this work, we present the results of low temperature heat capacity and inelastic neutron scattering studies of the sodalite (SOD) and diamondoid ( dia ) topologies of the popular zinc 2-methylimidazolate framework, Zn(MeIm) 2 . Molar heat capacities from 1.8 K to 300 K are presented, along with theoretical fits and the values of C p,m °, Δ 0 T S m °, Δ 0 T H m °, and Φ m ° calculated from those fits. The Gibbs energy of the transformation from SOD to dia is -(4.6 ± 2.2) kJ, and this transformation is primarily enthalpically driven. The results of this study are compared with previous measurements on the zinc 2-ethylimidazolate framework, Zn(EtIm) 2 . Inelastic neutron scattering measurements confirm the presence of low energy modes and suggest that the higher heat capacity of SOD at low temperatures is due to the dynamics of the methyl groups on the methylimidazolate linkers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Increased water availability at various timescales has different effects on stomatal closure point in isohydric piñon pine and anisohydric juniper

Abstract Stomatal Closure Point (SCP) has commonly been used to describe drought response strategies in plants, with isohydric species maintaining relatively high, constant SCP compared to anisohydric species that can lower SCP with increasing drought severity. However, there is evidence that, within these groups, SCP may respond dynamically to environmental conditions. Here, we explored how increasing water availability affects SCP in classically isohydric piñon pine and anisohydric one-seed or Utah juniper at various spatial- (i.e., from branch, to tree, to ecosystem) and temporal- (i.e., hours to decades) scales. Our results show that short-term increases in water availability decreased SCP in isohydric piñon pine, making it more anisohydric, while short-term rehydration had no effect on SCP in anisohydric juniper. Increasing mean annual precipitation, on the other hand, increased SCP in both species. Our findings are consistent with documented differences in the use of ABA to control stomata in iso- and aniso-hydric species on short timescales, and with structural acclimation in both species at long timescales. These results illustrate that the local environment plays a large role in determining SCP.

Kraklow, Vachel↗