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At least 1,153 records · Page 64
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Organic Molecules Mimic Alkali Metals Enabling Spontaneous Harpoon Reactions with Halogens

Abstract The harpoon mechanism has been a milestone in molecular reaction dynamics. Until now, the entity from which electron harpooning occurs has been either alkali metal atoms or non‐metallic analogs in their excited states. In this work, we demonstrate that a common organic molecule, octamethylcalix[4] pyrrole (omC4P), behaves just like alkali metal atoms, enabling the formation of charge‐separated ionic bonding complexes with halogens omC4P + ⋅ X − ( X =F−I, SCN) via the harpoon mechanism. Their electronic structures and chemical bonding were determined by cryogenic photoelectron spectroscopy of the corresponding anions and confirmed by theoretical analyses. The omC4P + ⋅ X − could be visualized to form from the reactants omC4P+ X via electron harpooning from omC4P to X at a distance defined by the energy difference between the ionization potential of omC4P and electron affinity of X .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Structural deformation and mechanical response of CrS 2 , CrSe 2 and Janus CrSSe

In the framework of density functional theory (DFT), we investigate the structural deformation, and mechanical behavior of the Janus CrSSe, which has out-of-plane structural asymmetry, with conventional transition metal dichalcogenides (TMDs) CrS 2 and CrSe 2 . The Janus CrSSe could be a potential candidate for machinable optoelectronic and piezoelectric applications. Here, we predict that these compounds are chemically, mechanically, and dynamically stable with the covalent bond between the TM(Cr) and chalcogen(X=S, Se) atoms. Due to the influence of tensile strain, the Cr–X bond length of each monolayers increases and the thickness decreases. Interestingly, the in-plane stiffness, shear and layer moduli, Poisson’s ratio, ultimate bi/uni-axial stress of Janus CrSSe are in between the values of CrS 2 and CrSe 2 monolayers. Similar to TMDs, the orientation-dependent in-plane stiffness and Poisson’s ratio demonstrates the isotropic behavior in Janus CrSSe. Furthermore, it can sustain a larger value of uni/bi-axial tensile strain with the critical strain equivalent to CrX 2 monolayers. By applying higher-order strain, we have also found average elastic–plastic behavior as expected. These findings demonstrate that the Janus CrSSe monolayer is a mechanically stable and ductile compound that maintains the hybrid behavior.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Solid breeder material crystal structure evolution due to Li burn up–Loss of crystal stability

Solid breeder materials for fusion power plants are subjected to extreme conditions of radiation damage, high temperature and designed component burn-up. Here, the loss of lattice stability of Li 2 TiO 3 due to Li burn-up was investigated using first principles-based approaches to aid evaluation of upper limit of component lifetime. The lattice stability is analyzed using calculated phonon dispersion in the Li 2 TiO 3 supercell, while Li burn-up is modeled by the introduction of Li-vacancies. It has been determined that the studied ceramic can be structurally stable up to ~40% of Li atoms burn-up. At 50% burn-up, the negative frequency branch in the phonon dispersion spectrum appears indicating the loss of lattice dynamical stability. Moreover, the structure obtained by introduction of unstable frozen phonons with minima energy amplitude also results in a phonon dispersion with negative branches in the structure obtained. Therefore, the system completely loses stability when approximately half of Li atoms are consumed.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Direct Observation of Electron Beam-Induced Phase Transition in MgCrMnO 4

Irreversible structural transformation in intercalation-type cathode materials, which has been frequently observed, has been perceived as a principal cause of capacity fading and voltage decay in (uni) multivalent batteries. Herein, we explored the electron beam-induced spinel to defective rocksalt phase transitions in MgCrMnO 4 , a potential multivalent cation intercalation cathode, using atomic-resolution imaging and spectroscopy in an aberration-corrected scanning transmission electron microscope. This dynamic electron beam irradiation study of specific structural transformations provides an atomistic understanding of the structural evolution observed in transition-metal oxide spinels during electrochemical cycling using multivalent cations, such as Mg 2+ . By combining an imaging study with first-principles modeling, we demonstrate that the mechanism of the spinel to defective rocksalt transformation in MgCrMnO 4 nanostructures is enabled by the presence of oxygen vacancies and is, therefore, very similar to that observed in transition-metal oxide spinels upon Li intercalation.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Low Energy Implantation into Transition-Metal Dichalcogenide Monolayers to Form Janus Structures

Atomically-thin two-dimensional (2D) materials face significant energy barriers for synthesis and processing into functional metastable phases such as Janus structures. Here, in this study, the controllable implantation of hyperthermal species from pulsed laser deposition (PLD) plasmas is introduced as a top-down method to compositionally engineer 2D monolayers. The kinetic energies of Se clusters impinging on suspended monolayer WS 2 crystals were controlled in the <10 eV/atom range with in situ plasma diagnostics to determine the thresholds for selective top layer replacement of sulfur by selenium for the formation of high quality WSSe Janus monolayers at low (300 °C) temperatures, and bottom layer replacement for complete conversion to WSe 2 . Atomic-resolution electron microscopy and spectroscopy in tilted geometry confirm the WSSe Janus monolayer. Molecular dynamics simulations reveal that Se clusters implant to form disordered metastable alloy regions, which then recrystallize to form highly ordered structures, opening the door for low-energy implantation by PLD as a novel method to explore the synthesis of 2D Janus layers and alloys of variable composition.

2D materials↗
DOE OSTI2024

Small, solubilized platinum nanocrystals consist of an ordered core surrounded by mobile surface atoms

In situ structures of Platinum (Pt) nanoparticles (NPs) can be determined with graphene liquid cell transmission electron microscopy. Atomic-scale three-dimensional structural information about their physiochemical properties in solution is critical for understanding their chemical function. We here analyze eight atomic-resolution maps of small (<3 nm) colloidal Pt NPs. Their structures are composed of an ordered crystalline core surrounded by surface atoms with comparatively high mobility. 3D reconstructions calculated from cumulative doses of 8500 and 17,000 electrons/pixel, respectively, are characterized in terms of loss of atomic densities and atomic displacements. Less than 5% of the total number of atoms are lost due to dissolution or knock-on damage in five of the structures analyzed, whereas 10–16% are lost in the remaining three. Less than 5% of the atomic positions are displaced due to the increased electron irradiation in all structures. The surface dynamics will play a critical role in the diverse catalytic function of Pt NPs and must be considered in efforts to model Pt NP function computationally.

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

An atomic cluster expansion (ACE) potential for water under extreme conditions

We present a machine learning interatomic potential for water designed to capture its complex multiphase behavior, including both molecular and superionic ice phases. The potential is based on the atomic cluster expansion (ACE) formulation and has been parameterized to enable high-fidelity molecular dynamics simulations of water under extreme conditions, for pressures up to 100 GPa and for temperatures between 500 and 6000 K. A diverse range of configurations was generated through ab initio molecular dynamics (AI-MD) simulations, covering insulating and superionic ice phases, liquid water, and dissociated plasma phase. We demonstrate that the H 2 O ACE potential accurately reproduces experimental and DFT predicted isotherms and Hugoniots. Crucially, the potential is able to capture the intricate phase behavior of water, including the transition from molecular fluid to the appropriate solid ice phases, and the superionic ice phases. This work provides a robust interatomic potential that can be used for large-scale, accurate simulations of water under extreme thermodynamic conditions.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Disorder-induced heating in molecular atmospheric pressure plasmas

Abstract Recent work has shown that ions are strongly coupled in atmospheric pressure plasmas when the ionization fraction is sufficiently large, leading to a temperature increase from disorder-induced heating (DIH) that is not accounted for in standard modelling techniques. Here, we extend this study to molecular plasmas. A main finding is that the energy gained by ions in DIH gets spread over both translational and rotational degrees of freedom on a nanosecond timescale, causing the final ion and neutral gas temperatures to be lower in the molecular case than in the atomic case. A model is developed for the equilibrium temperature that agrees well with molecular dynamics simulations. The model and simulations are also applied to pressures up to ten atmospheres. We conclude that DIH is a significant and predictable phenomena in molecular atmospheric pressure plasmas.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2022

Sweep-tracing algorithm: in silico slip crystallography and tension-compression asymmetry in BCC metals

Abstract Direct Molecular Dynamics (MD) simulations are being increasingly employed to model dislocation-mediated crystal plasticity with atomic resolution. Thanks to the dislocation extraction algorithm (DXA), dislocation lines can be now accurately detected and positioned in space and their Burgers vector unambiguously identified in silico, while the simulation is being performed. However, DXA extracts static snapshots of dislocation configurations that by themselves present no information on dislocation motion. Referred to as a sweep-tracing algorithm (STA), here we introduce a practical computational method to observe dislocation motion and to accurately quantify its important characteristics such as preferential slip planes (slip crystallography). STA reconnects pairs of successive snapshots extracted by DXA and computes elementary slip facets thus precisely tracing the motion of dislocation segments from one snapshot to the next. As a testbed for our new method, we apply STA to the analysis of dislocation motion in large-scale MD simulations of single crystal plasticity in BCC metals. We observe that, when the crystal is subjected to uniaxial deformation along its [001] axis, dislocation slip predominantly occurs on the {112} maximum resolved shear stress plane under tension, while in compression slip is non-crystallographic (pencil) resulting in asymmetric mechanical response. The marked contrast in the observed slip crystallography is attributed to the twinning/anti-twinning asymmetry of shears in the {112} planes relatively favoring dislocation motion in the twinning sense while hindering dislocations from moving in the anti-twinning directions.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Spectroscopic and Dynamical Studies of Highly Energized Small Polyatomic Molecules (End-of-Grant Report)

The aim of this research program has been to develop models for qualitative and quantitative understanding of complex processes in small molecules, such as vibronic coupling, predissociation, photodissociation, and isomerization. Simple models capture physical insights and lead to intuitive ideas that can enlighten a broad array of problems. Numerical fits can provide predictive power, but rarely impart insights into the underlying mechanisms responsible for the observed phenomena. This DOE supported program has prioritized a quantum mechanical understanding over a perfect numerical fit of spectra. Finding few-parameter models, when those parameters have physical meaning, allows the insights gained from one problem to be easily applied to related problems in other systems. The systems that have been under investigation include atmospherically relevant sulfur-containing compounds, various unimolecular dynamical processes of electronically excited acetylene, and the rovibrational dynamics of formaldehyde and SO 2 .

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2026

Integrative computational investigation of the spectroscopy, dynamics, and controlling of molecular excitons in complex environments (Final Technical Report)

The major goal of this research project was to advance theoretical and computational capability to describe the dynamics and the spectroscopy of molecular excitons as reliably and efficiently as possible. Outcomes of the project contributed to new understanding of the interaction between light and molecular materials and ensuing dynamics of excited electronic states. These can assist experimentalists in developing novel methods to utilize quantum properties of molecules and molecular excitons for new energy harvesting and quantum information processing.

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

Dynamic Metal–Support Interaction Dictates Cu Nanoparticle Sintering on Al 2 O 3 Surfaces

Nanoparticle sintering remains a critical challenge in heterogeneous catalysis. In this work, we present a unified deep potential (DP) model based on the Perdew–Burke–Ernzerhof approximation of density functional theory for Cu nanoparticles on three Al 2 O 3 surfaces (γ-Al 2 O 3 (100), γ-Al 2 O 3 (110), and α-Al 2 O 3 (0001)). Using DP-accelerated simulations, we reveal that the nanoparticle size-mobility relationship strongly depends on the supporting surface. The diffusion of nanoparticles on the two γ-Al 2 O 3 surfaces is almost independent of the size of the nanoparticle, while the diffusion on α-Al 2 O 3 (0001) decreases rapidly with increasing size. Interestingly, nanoparticles with fewer than 55 atoms diffuse several times faster on α-Al 2 O 3 (0001) than on γ-Al 2 O 3 (100) at 800 K while expected to be more sluggish based on their larger binding energy at 0 K. The diffusion on α-Al 2 O 3 (0001) is facilitated by dynamic metal–support interaction (MSI), where Al atoms move out of the surface plane to optimize contact with the nanoparticle and relax back to the plane as the nanoparticle moves away. In contrast, the MSI on γ-Al 2 O 3 (100) and on γ-Al 2 O 3 (110) is dominated by more stable and directional Cu–O bonds, consistent with the limited diffusion observed on these surfaces. Our extended MD simulations provide insight into the sintering processes, showing that the dispersity of the nanoparticles strongly influences the coalescence driven by nanoparticle diffusion. We observed that the coalescence of Cu 13 nanoparticles on α-Al 2 O 3 (0001) can occur in a short time (10 ns) at 800 K even with an initial internanoparticle distance increased to 3 nm, while the coalescence on the two γ-Al 2 O 3 surfaces are inhibited significantly by increasing the initial internanoparticle distance. These findings demonstrate that the dynamics of the supporting surface is crucial to understanding the sintering mechanism and offer guidance for designing sinter-resistant catalysts by engineering the support morphology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Diabatic Valence-Hole States in the C 2 Molecule: “Putting Humpty Dumpty Together Again”

Despite the long history of spectroscopic studies of the C$_2$ molecule, fundamental questions about its chemical bonding are still being hotly debated. The complex electronic structure of C$_2$ is a consequence of its dense manifold of near-degenerate, low-lying electronic states. A global multi-state diabatic model is proposed here to disentangle the numerous configuration interactions within four symmetry manifolds of C$_2$ ($^{1}\Pi_g$, $^{3}\Pi_g$, $^{1}\Sigma_u^+$, and $^{3}\Sigma_u^+$). The key concept of our model is the existence of two "valence-hole" configurations, $2\sigma_g^22\sigma_u^11\pi_{u}^33\sigma_g^2$ for $^{1,3}\Pi_g$ states and $2\sigma_g^22\sigma_u^11\pi_{u}^43\sigma_g^1$ for $^{1,3}\Sigma_u^+$ states that derive from $3\sigma_g\leftarrow2\sigma_u$ electron promotion. The lowest-energy state from each of the four C$_2$ symmetry species is dominated by this type of valence-hole configuration at its equilibrium internuclear separation. Finally, as a result of their large binding energy (nominal bond order of 3) and correlation with the 2s$^2$2p$^2$+2s2p$^3$ separated-atom configurations, the presence of these valence-hole configurations has a profound impact on the $global$ electronic structure and unimolecular dynamics of C$_2$.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Exploring poly-crystallization in semiconductors through assumption-less growth simulations: CdTe/CdS case study

Crystal growth is a complex process with far-reaching implications for high-performance materials across various fields. Recent advancements in structural analysis methods such as polyhedral template matching, which allows semiconductor-specific analysis, coupled with simulation technology, have enabled the comprehensive study of crystallization dynamics in semiconductors. However, the exploration of polycrystalline semiconductors created with minimal external intervention of the crystallization processes is relatively uncharted in comparison with metals. In this study, we employ molecular dynamics to simulate the growth of polycrystalline CdTe/CdS with the assumptions of classical mechanics, a Stillinger–Weber potential, an amorphous substrate, and common vapor growth conditions to allow the polycrystalline structures to evolve naturally. Post-simulation, we identify and analyze impactful structures and events, comparing them to theory and experiment to gain insight into various modes of crystallization dynamics. Two research questions guided the study: (1) How realistic are assumption-less simulated polycrystalline semiconductor structures? (2) To what extent can the approach provide insight into crystallization? The simulations, performed with minimal external control, yield polycrystalline structures mirroring experimental findings. The analysis reveals key crystallization insights, such as the role of amorphous atoms in the transition from nucleation to grain growth and the transformative impact of single events, such as dislocations, on crystallization dynamics. The method paves the way for reproducing and analyzing realistic polycrystalline semiconductor structures with minimal simulation assumptions across various growth modes.

Abdullah, Sharmin↗
DOE OSTI2024

Reversible Phasonic Control of a Quantum Phase Transition in a Quasicrystal

Periodic driving can tune the quasistatic properties of quantum matter. A well-known example is the dynamical modification of tunneling by an oscillating electric field. Here we show experimentally that driving the phasonic degree of freedom of a cold-atom quasicrystal can continuously tune the effective quasidisorder strength, reversibly toggling a localization-delocalization quantum phase transition. Measurements agree with fit-parameter-free theoretical predictions, and illuminate a fundamental connection between Aubry-André localization in one dimension and dynamic localization in the associated two-dimensional Harper-Hofstadter model. These results open up new experimental possibilities for dynamical coherent control of quantum phase transitions.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2024

The development of thermodynamically consistent and physics-informed equation-of-state model through machine learning

Ab initio molecular dynamics (AIMD) simulations have become an important tool used in the construction of equations of state (EOS) tables for warm dense matter. Due to computational costs, only a limited number of system state conditions can be simulated, and the remaining EOS surface must be interpolated for use in radiation-hydrodynamic simulations of experiments. In this work, we develop a thermodynamically consistent EOS model that utilizes a physics-informed machine learning approach to implicitly learn the underlying Helmholtz free-energy from AIMD generated energies and pressures. The model, referred to as PIML-EOS, was trained and tested on warm dense polystyrene producing a fit within a 1% relative error for both energy and pressure and is shown to satisfy both the Maxwell and Gibbs–Duhem relations. In addition, we provide a path toward obtaining thermodynamic quantities, such as the total entropy and chemical potential (containing both ionic and electronic contributions), which are not available from current AIMD simulations.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2024

Modeling bicarbonate formation in an alkaline solution with multi-level quantum mechanics/molecular dynamics simulations

Understanding carbonate speciation and how it may be modulated is essential for the advancement of carbon dioxide (CO 2 ) capture and storage technologies, which often rely on the transformation of CO 2 into carbonate, e.g. via the formation of carbonate minerals. To date, few atomic-level, quantum-mechanics-based simulations have been carried out to characterize how carbonic acid (H 2 CO 3 ) and bicarbonate ($HCO^{-}_{3}$) form in aqueous solution, and how pH affects this process. Recently, Martirez and Carter utilized rare-event sampling density functional theory molecular dynamics simulations in combination with multi-level embedded correlated wavefunction theory, thus accounting for both solvent dynamics and electron correlation accurately, to elucidate the mechanism of H 2 CO 3 formation in neutral solution (J. Am. Chem. Soc., 145, 12561, 2023). Here, we perform a complementary simulation using the same method to map out the energetics of $HCO^{-}_{3}$ formation from dissolved CO 2 in basic solution. We find that, as in H 2 CO 3 formation, including water dynamics is important to obtain an accurate prediction of the energetics for the aforementioned reaction. Furthermore, only with MD did we identify the correct pathway for the reaction, in which water – not hydroxide – acts as the initial nucleophile and only at the transition state does it lose a proton.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2021

Energetics of polymeric carbon monoxide

The transformation of carbon monoxide (CO) from a molecular liquid to a polymeric solid under isothermal compression at room temperature is investigated using first principles theory. We report structural and thermodynamic properties from ambient density up to 2.45 g/cc obtained using density functional theory molecular dynamics simulations, including hybrid exchange corrections. The theoretical results are compared with newly obtained polymeric CO samples, synthesized in a large volume press. The explosive performance of polymeric CO is predicted and discussed. Under most favorable assumptions, it is found to be comparable to trinitrotoluene.

25 ENERGY STORAGE↗