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At least 91 records · Page 5

Discovery of tunable and soluble organic emitters for solid-state lasers with a self-driving laboratory

We have recently demonstrated the ability of using self-driving laboratories for AI-driven searches of organic emitters for solid-state lasing devices. Our past workflow featured solubility challenges for such large molecular moieties. In this next-generation study, we return to the drawing board to explore a family of com-pounds that are much solution processable and composed of a set of electronic cores that provide a broader color response. Out of 252 potential candidates,and with guidance from DFT calculations, we selectively perform a compre-hensive study exploring 51 fluorene-based A-B-A type organic laser oligomers, armed with our self-driving lab. The candidates range from simple hydrocarbon molecules to complex hetero atom-mixed molecules. As a result of this study, we highlight diketopyrrolopyrrole and benzodiazole derivatives for their largely red-shifted emissions. Furthermore, we investigate the effect of color change aris-ing from hetero atom permutation, fluorine addition, thiophene coupling, and a combination of fluorine addition and thiophene coupling. Amplified spontaneous emission (ASE) measurements in the solid state further corroborate the lasing potential of selected candidates, reinforcing their suitability for future device applications. The computational study with density functional theory confirms the experimental results.

fluorescence↗

Development of neural network force fields for corrosion studies

To fully understand the chemistry and physics of corrosion, novel methods of simulation must be developed. One approach is designing machine learning (ML) algorithms integrated with density functional theory to develop adaptive force fields to gain insight into corrosion behavior namely at the surface of metal oxides. Current methods of modeling corrosion are slow due to the computational cost of resolving both reaction mechanics and mass transport processes. Machine learning methods can be implemented to obtain structure-activity relationships at both the molecular and bulk scale while still retaining the accuracy of density functional theory (DFT) and significantly decreasing the time needed for simulations of complex chemical processes in the various environments of corrosion. Multiscale models are needed for corrosion studies to fully understand its processes not only at the atomic length scale (chemical bonding, energies, and forces), but also at the nano and meso length scales (solid-state physics and material science processes). Current methods of study include DFT, molecular dynamics, and Monte Carlo. The limitation of DFT is that only a small number of atoms or molecules can be simulated at that level of theory. Density functional theory is used to study the electronic structure of atoms and molecules, and calculate the force component of each atom. However, these calculations are limited to about 1000 atoms. Custom periodic boundary conditions (PBC) can be used to describe the various environments and defects that affect the atomic forces to produce a large data set from which a training set can be derived. Machine learning can be utilized to overcome the barrier of modeling macroscopic and multi-scale processes from ab initio calculations through the development of adaptive force fields. Local environments determine the atomic forces of a given system, therefore adaptive force fields must be created to produce reliable quantum mechanical calculations. This can be achieved by developing a learning algorithm that uses the mapped atomic forces or fingerprint as an input to produce energies and magnetic moments as output. A systematic approach was used to begin to build a data set in order to accurately describe the atomic forces in various environments. In Figure 4 below, a simple PBC cell of Fe{sub 2}O{sub 3} was first optimized. A surface optimization was performed next, followed by a hydroxylated surface optimization. Once this calculation has converged, the adsorption of halide species to the hydroxylated surface will be investigated. TensorFlow is an open source platform for machine learning developed by Google. Using a high level application program interface (API) such as Keras allows for building and training ML models easily in a number of different environments and languages. For this project, a neural network was developed within Anaconda in Python. Future Work: Further development of reference data set; Refining neural network and learning algorithm; Fingerprinting atomic environment to enable mapping of atomic force components; Choosing appropriate training set from reference data; Learning from training set and enabling non-linear mapping of training set fingerprints and the atomic forces; Estimation of uncertainty to identify ranges of outside applicability; Testing and analysis of molecular dynamic simulations.

36 MATERIALS SCIENCE↗

Benchmarking Correlation-Consistent Basis Sets for Frequency-Dependent Polarizabilities with Multiresolution Analysis

This paper presents the first converged frequency-dependent HF polarizability results for general molecules, on a set of 89 closed-shell atoms and molecules. The solver employs multiresolution analysis (MRA) in a multiwavelet basis to compute both ground and response states to a guaranteed precision, which are validated against independent numerical grid calculations on atoms and linear molecules. The MRA ground-state energies and response properties are used to evaluate results in correlation-consistent basis sets up to 5Z augmented with either single or double diffuse functions and core-polarization functions. Systematic trends are revealed through consideration of chemical composition as well as the use of machine learning to cluster convergence trends, the latter suggesting the possibility of learning and correcting basis-set error.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Single-Atom Doping at the Molecule–Metal Interface: How Rh Affects Surface Explosion Kinetics

Controlling chemical reactions at interfaces is central to many fields, including atmospheric, environmental, and biological chemistry as well as catalysis and corrosion. We performed a fundamental study of how catalytically active Rh atoms placed at and above a molecule-metal interface influence the surface reaction kinetics of tartaric acid (TA) decomposition. Specifically, TA decomposition on Cu(100) exhibits autocatalytic decomposition kinetics involving a slow initiation step followed by fast decomposition of the molecular layer. These so-called “surface explosions” are extremely sensitive to initial conditions, making it fundamentally interesting to study how the placement of reactive atoms affects the reaction rate. Temperature-programmed reaction (TPR) experiments reveal that Rh atoms embedded in the Cu(100) surface beneath TA (TA/Rh/Cu) or atop the TA layer (Rh/TA/Cu) reduce the decomposition temperature and modify the reaction rate constants. Isothermal TPR analysis reveals that Rh enhances both the initiation rate constant, k i , and the explosion rate constant, k e , facilitating explosive decomposition at lower temperatures. This result provides evidence that both the initiation and explosion steps occur at the metal-molecule interface and are accelerated by the presence of Rh at this interface. This study illustrates how small amounts of reactive elements may be used to control nonlinear kinetic processes at interfaces.

desorption↗

Quantum chemical topology and natural bond orbital analysis of M–O covalency in M(OC 6 H 5 ) 4 (M = Ti, Zr, Hf, Ce, Th, Pa, U, Np)

Covalency is complex yet central to our understanding of chemical bonding, particularly in the actinide series. In this work, we assess covalency in a series of isostructural d and f transition element compounds M(OC 6 H 5 ) 4 (M = Ti, Zr, Hf, Ce, Th, Pa, U, Np) using scalar relativistic hybrid density functional theory in conjunction with the Natural Bond Orbital (NBO), quantum theory of atoms in molecules (QTAIM) and interacting quantum atoms (IQA) approaches. The IQA exchange–correlation covalency metric is evaluated for the first time for actinides other than uranium, in order to assess its applicability in the 5f series. It is found to have excellent correlation with NBO and QTAIM covalency metrics, making it a promising addition to the computational toolkit for analysing metal–ligand bonding. Our range of metrics agree that the actinide-oxygen bonds are the most covalent of the elements studied, with those of the heavier group 4 elements the least. Within the early actinide series, Th stands apart from the other three elements considered, being consistently the least covalent.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Format Proposal for Isotopic Distribution in TSL Files for ENDF/B-VIII.1 [Slides]

This presentation proposes a format of an ‘footer’ file for ENDF6-format TSL files. This would contain several pieces of pertinent information for the scattering atom. such as the Number of scattering atoms in molecule, Isotopic distribution within scattering atom, and free atom and atomic weight ratios for each isotope. This setup will not require significant changes to processing codes or to other sections of the MF7 file.

07 ISOTOPE AND RADIATION SOURCES↗

Solid state core-exciton dynamics in NaCl observed by tabletop attosecond four-wave mixing spectroscopy

Nonlinear wave mixing in solids with ultrafast x-rays can provide insight into complex electronic dynamics of materials. Here, tabletop-based attosecond noncollinear four-wave mixing (FWM) spectroscopy using one extreme ultraviolet (XUV) pulse from high harmonic generation and two separately timed few-cycle near-infrared (NIR) pulses characterizes the dynamics of the Na + L 2,3 edge core-excitons in NaCl around 33.5 eV. An inhomogeneous distribution of core-excitons underlying the well-known doublet absorption of the Na+ Γ point core-exciton spectrum is deconvoluted by the resonance-enhanced nonlinear wave mixing spectroscopy. In addition, other dark excitonic states that are coupled to the XUV-allowed levels by the NIR pulses are characterized spectrally and temporally. Approximately <10fs coherence lifetimes of the core-exciton states are observed. Furthermore, the core-excitonic properties are discussed in the context of strong electron-hole exchange interactions, electron-electron correlation, and electron-phonon broadening. This investigation successfully indicates that tabletop attosecond FWM spectroscopies represent a viable technique for time-resolved solid state measurements.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Conveyor-belt magneto-optical trapping of molecules

Abstract Laser cooling is used to produce ultracold atoms and molecules for quantum science and precision measurement applications. Molecules are more challenging to cool than atoms due to their vibrational and rotational internal degrees of freedom. Molecular rotations lead to the use of type-II transitions ( F ⩾ F ′ ) for magneto-optical trapping (MOT). When typical red detuned light frequencies are applied to these transitions, sub-Doppler heating is induced, resulting in higher temperatures and larger molecular cloud sizes than realized with the type-I MOTs most often used with atoms. To improve type-II MOTs, Jarvis et al (2018 Phys. Rev. Lett. 120 083201) proposed a blue-detuned MOT to be applied after initial cooling and capture with a red-detuned MOT. This was successfully implemented (Burau et al 2023 Phys. Rev. Lett. 130 193401; Jorapur et al 2024 Phys. Rev. Lett. 132 163403; Li et al 2024 Phys. Rev. Lett. 132 233402), realizing colder and denser molecular samples. Very recently, Hallas et al (2024 arXiv:2404.03636) demonstrated a blue-detuned MOT with a ‘1+2’ configuration that resulted in even stronger compression of the molecular cloud. Here, we describe and characterize theoretically the conveyor-belt mechanism that underlies this observed enhanced compression. We perform numerical simulations of the conveyor-belt mechanism using both stochastic Schrödinger equation and optical Bloch equation approaches. We investigate the conveyor-belt MOT characteristics in relation to laser parameters, g -factors and the structure of the molecule, and find that conveyor-belt trapping should be applicable to a wide range of laser-coolable molecules.

Li, Grace K. (ORCID:0000000277223355)↗

Tunable pairing with local spin-dependent Rydberg molecule potentials in an atomic Fermi superfluid

We explore the energy spectrum and eigenstates of two-component atomic Fermi superfluids with tunable pairing interactions in the presence of spin-dependent ultralong-range Rydberg molecule (ULRM) potentials, within the Bogoliubov–de Gennes formalism. The attractive ULRM potentials lead to local-density accumulation, while their difference results in a local polarization potential and induces the in-gap Yu-Shiba-Rusinov (YSR) states whose energies lie below the bulk energy gap. A transition from equal population to population imbalance occurs as the pairing strength falls below a critical value, accompanied by the emergence of local Fulde-Ferrell-Larkin-Ovchinnikov (FFLO)–like states characterized by out-of-phase wave functions and lower energies compared to the YSR states. The negative contribution emanating from the FFLO-like states also causes a sign change in the gap function within the ULRM potentials. Depending on the Rydberg excitation, the transition towards population imbalance can be on either the BCS or the Bose-Einstein condensation side of the Fermi superfluid. Additionally, spin-polarized bound states arise along with oscillatory “clumpy states” to compensate for the local-density difference. Here, we discuss possible experimental realizations of the composite Rydberg-atom–Fermi-superfluid system.

Cold and ultracold molecules↗

Coherent Reaction between Molecular and Atomic Bose-Einstein Condensates: Integrable Model

Here, we solve a model that describes a stimulated conversion between ultracold bosonic atoms and molecules. The reaction is triggered by a linearly time-dependent transition throughout the Feshbach resonance. Our solution predicts a dependence, with a dynamic phase transition, of the reaction efficiency on the transition rate for both atoms-to-molecule pairing and molecular dissociation processes. We find that for the latter process with a linear energy dispersion of atomic modes, the emerging phase can have a thermalized energy distribution of noninteracting bosons with the temperature defined by the rate of the transition. This provides a simple interpretation of the phase transition in terms of the creation of equilibrium Bose-Einstein condensate.

74 ATOMIC AND MOLECULAR PHYSICS↗

Framework for simulating gauge theories with dipolar spin systems

Gauge theories appear broadly in physics, ranging from the standard model of particle physics to long-wavelength descriptions of topological systems in condensed matter. However, systems with sign problems are largely inaccessible to classical computations and also beyond the current limitations of digital quantum hardware. In this work, we develop an analog approach to simulating gauge theories with an experimental setup that employs dipolar spins (molecules or Rydberg atoms). We consider molecules fixed in space and interacting through dipole-dipole interactions, avoiding the need for itinerant degrees of freedom. Each molecule represents either a site or gauge degree of freedom, and Gauss's law is preserved by a direct and programmatic tuning of positions and internal state energies. This approach can be regarded as a form of analog systems programming and charts a path forward for near-term quantum simulation. As a first step, we numerically validate this scheme in a small-system study of U(1) quantum link models in (1+1) dimensions with link spin S = 1/2 and S =1 and illustrate how dynamical phenomena such as string inversion and string breaking could be observed in near-term experiments. Our work brings together methods from atomic and molecular physics, condensed matter physics, high-energy physics, and quantum information science for the study of nonperturbative processes in gauge theories.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Linear polarization fractions of Fulcher- α fluorescence in electron collisions with H 2

We apply the molecular convergent close-coupling method to the calculation of linear polarization fractions for Fulcher-band fluorescence following electron-impact excitation of the H 2 d 3 Π u state. Furthermore, the results exhibit the opposite threshold behavior compared to the only previous calculations, but are in agreement with the most recent measurements for the Q(1), R(1), and Q(3) transitions.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Vapor-Cell-Based Atomic Electrometry for Detection Frequencies below 1 kHz

Rydberg-assisted atomic electrometry using alkali-metal atoms contained inside a vacuum environment for detecting external electric fields at frequencies below a few kilohertz has been quite challenging due to the low-frequency electric-field-screening effect that is caused by the alkali-metal atoms adsorbed on the inner surface of the container. In this work, we report a very slow electric-field-screening phenomenon with a timescale up to the order of seconds on a rubidium-vapor cell that is made of monocrystalline sapphire. Furthermore, using this sapphire rubidium-vapor cell with an optically induced, internal bias electric field, we demonstrate vapor-cell-based, low-frequency atomic electrometry that responds to the electric field strength linearly. Limited by the given experimental conditions, this demonstrated atomic electrometer uses an active volume of 11 mm 3 and delivers a spectral noise floor of around 0.34 mV/m √Hz and a 3-dB low cutoff frequency of around 770 Hz inside the vapor cell. This work investigates a regime of vapor-cell-basedatomic electrometry that was seldom studied before, which may enable more applications that use atomicelectric-field-sensing technology.

74 ATOMIC AND MOLECULAR PHYSICS↗

Probing the Potential Energy Profile of the I + (H 2 O) 3 → HI + (H 2 O) 2 OH Forward and Reverse Reactions: High Level CCSD(T) Studies with Spin-Orbit Coupling Included

Three different pathways for the atomic iodine plus water trimer reaction I + (H 2 O) 3 → HI + (H 2 O) 2 OH were preliminarily examined by the DFT-MPW1K method. Related to previous predictions for the F/Cl/Br + (H 2 O) 3 reactions, three pathways for the I + (H 2 O) 3 reaction are linked in terms of geometry and energetics. To legitimize the results, the “gold standard” CCSD(T) method was employed to investigate the lowest-lying pathway with the correlation-consistent polarized valence basis set up to cc-pVQZ(-PP). According to the CCSD(T)/cc-pVQZ(-PP)//CCSD(T)/cc-pVTZ(-PP) results, the I + (H 2 O) 3 → HI + (H 2 O) 2 OH reaction is predicted to be endothermic by 47.0 kcal mol -1 . The submerged transition state is predicted to lie 43.7 kcal mol -1 above the separated reactants. The I···(H 2 O) 3 entrance complex lies below the separated reactants by 4.1 kcal mol -1 , and spin-orbit coupling has a significant impact on this dissociation energy. The HI···(H 2 O) 2 OH exit complex is bound by 4.3 kcal mol -1 in relation to the separated products. Compared with simpler I + (H 2 O) 2 and I + H 2 O reactions, the I + (H 2 O) 3 reaction is energetically between them in general. It is speculated that the reaction between the iodine atom and the larger water clusters may be energetically analogous to the I + (H 2 O) 3 reaction. The iodine reaction I + (H 2 O) 3 is connected with the analogous valence isoelectronic bromine/chlorine reactions Br/Cl + (H 2 O) 3 but much different from the F + (H 2 O) 3 reaction. Significant difference with other halogen systems, especially for barrier heights, are seen for the iodine systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Efficient Intermolecular Energy Exchange and Soft-ionization of Water at Nanoplatelet Interfaces

X-ray, energetic photon and electron irradiation can ionize and electronically excite target atoms and molecules. These excitations undergo complicated relaxation and energy transfer processes that ultimately determine the manifold of system responses to the deposited excess energy. In weakly bound gas- and solution-phase samples, intermolecular Coulomb decay (ICD) and electron-transfer mediated decay (ETMD) can occur with neighboring atoms or molecules leading to efficient transfer of the excess energy to the surroundings. In ionic solids such as metal-oxides, intra- and inter-atomic Auger decay produces localized final states that lead to lattice damage and typically removal of cations from the substrate. The relative importance of Auger stimulated damage (ASD) versus ICD and ETMD in micro-solvated nanoparticle interfaces is not known. Though ASD is generally expected, essentially no lattice damage and very efficient ICD and ETMD resulting from ionization and electronic excitation of micro-solvated boehmite (AlOOH) nanoplatelets has been observed. Efficient energy transfer and soft ionization of interfacial molecules is likely a general phenomenon at gas-oxyhydroxide nanoparticle interfaces where the density of states of the ionized chemisorbed species significantly overlap the core hole states of the solid.

Jones, Brant M.↗

Relativistic Effects From Coupled-Cluster Theory

We discuss the theory and computational challenges of the relativistic coupled-cluster methods. Example calculations of heavy-atom-containing molecules are then presented to demonstrate the importance of scalar-relativistic, spin-orbit coupling, and electron-correlation effects on molecular properties as well as the applicability and usefulness of relativistic coupled-cluster methods in calculations aiming at high-accuracy results. Here, a unique applicability of the spinor-based relativistic coupled-cluster methods is also highlighted using the calculations of open shell actinide-containing small molecules. As a result, a summary is given together with an outlook into future developments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗