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Cryogenic growth of aluminum: Structural morphology, optical properties, superconductivity, and microwave dielectric loss

We explore the molecular beam epitaxy synthesis of superconducting aluminum thin films grown on c-plane sapphire substrates at cryogenic temperatures of 6 K and compare their behavior with films synthesized at room temperature. We demonstrate that cryogenic growth increases structural disorder, producing crystalline grains that modify the optical, electrical, and superconducting properties of aluminum. We observe that cryogenic deposition changes the color of aluminum from fully reflective to yellow and correlate the pseudodielectric function and reflectance with structural changes in the film. We find that smaller grain sizes enhance the superconductivity of aluminum, increasing its critical temperature and critical field. We then estimate the superconducting gap and coherence length of Cooper pairs in aluminum in the presence of disorder. In conclusion, we fabricate superconducting microwave resonators on these films and find that, independently of the growth temperature, the system is dominated by two-level system loss with similar quality factors in the high- and low-power regimes. We further measure a higher kinetic inductance in the cryogenically grown films.

36 MATERIALS SCIENCE↗

Silicon-Lattice-Matched Boron-Doped Gallium Phosphide: A Scalable Acousto-Optic Platform

The compact size, scalability, and strongly confined fields in integrated photonic devices enable new functionalities in photonic networking and information processing, both classical and quantum. Gallium phosphide (GaP) is a promising material for active integrated photonics due to its high refractive index, wide bandgap, strong nonlinear properties, and large acousto-optic figure of merit. Here, this study demonstrates that silicon-lattice-matched boron-doped GaP (BGaP), grown at the 12-inch wafer scale, provides similar functionalities as GaP. BGaP optical resonators exhibit intrinsic quality factors exceeding 25,000 and 200,000 at visible and telecom wavelengths, respectively. It further demonstrates the electromechanical generation of low-loss acoustic waves and an integrated acousto-optic (AO) modulator. High-resolution spatial and compositional mapping, combined with ab initio calculations, indicate two candidates for the excess optical loss in the visible band: the silicon-GaP interface and boron dimers. These results demonstrate the promise of the BGaP material platform for the development of scalable AO technologies at telecom and provide potential pathways toward higher performance at shorter wavelengths.

36 MATERIALS SCIENCE↗

Modulating Operational Conditions to Mitigate Deactivation in Formate Dehydrogenation on Pd Phases

In heterogeneous catalysis, poisoning by surface-bound intermediates poses a major barrier to sustained catalyst performance in (de)hydrogenation reactions. Formate/bicarbonate systems, as liquid organic hydrogen carriers (LOHCs), offer a CO 2 -integrated, low-temperature pathway for hydrogen storage and release, making them attractive for circular energy applications. However, their lower hydrogen density and susceptibility to catalyst deactivation limit their competitiveness compared to conventional LOHCs like methylcyclohexane. Here, this study investigates the mechanistic origins of formate (HCOO – ) dehydrogenation and associated deactivation on Pd interfaces. Using density functional theory (DFT) simulations, we show that under thermocatalytic conditions, strongly bound formate accumulates on the catalyst surface (Pd(111)), blocking active sites, raising activation barriers, and leading to progressive performance loss. Because formate adsorption involves charge transfer, we exploit its sensitivity to electronic structure by modulating the electrochemical potential of the catalyst. Our results reveal that hydrogen transfer from water and formate exhibits opposing potential dependencies, providing insights into the opposing driving forces behind both catalytic activity and poisoning. To further probe this phenomenon, we examine electrochemically induced phase transitions in Pd, focusing on PdO(100) and PdH(110), which are stable under oxidizing and reducing potentials, respectively, and demonstrate enhanced dehydrogenation activity between −0.4 and 0.2 V vs standard hydrogen electrode (SHE). Complementary thermal treatments help decouple kinetic and thermodynamic contributions to intermediate binding. These findings underscore the critical role of the catalyst phase and external stimuli in dictating poison-active site interactions and highlight phase engineering as a promising strategy to mitigate deactivation. This work offers mechanistic insights and design principles for developing more resilient and efficient catalysts for LOHC applications under realistic operating conditions.

Pd phase↗

Genome-resolved metagenomics reveals role of iron metabolism in drought-induced rhizosphere microbiome dynamics

Recent studies have demonstrated that drought leads to dramatic, highly conserved shifts in the root microbiome. At present, the molecular mechanisms underlying these responses remain largely uncharacterized. Here we employ genome-resolved metagenomics and comparative genomics to demonstrate that carbohydrate and secondary metabolite transport functionalities are overrepresented within drought-enriched taxa. These data also reveal that bacterial iron transport and metabolism functionality is highly correlated with drought enrichment. Using time-series root RNA-Seq data, we demonstrate that iron homeostasis within the root is impacted by drought stress, and that loss of a plant phytosiderophore iron transporter impacts microbial community composition, leading to significant increases in the drought-enriched lineage, Actinobacteria. Finally, we show that exogenous application of iron disrupts the drought-induced enrichment of Actinobacteria, as well as their improvement in host phenotype during drought stress. Collectively, our findings implicate iron metabolism in the root microbiome’s response to drought and may inform efforts to improve plant drought tolerance to increase food security.

59 BASIC BIOLOGICAL SCIENCES↗

Optimizing structured surfaces for diffractive waveguides

We introduce universal diffractive waveguide designs that can match the performance of conventional dielectric waveguides and achieve various functionalities. Optimized using deep learning, diffractive waveguides can be cascaded to form any desired length and are comprised of transmissive diffractive surfaces that permit the propagation of desired modes with low loss and high mode purity. In addition to guiding the targeted modes through cascaded diffractive units, we also developed various waveguide components and introduced bent diffractive waveguides, rotating the direction of mode propagation, as well as spatial and spectral mode filtering and mode splitting diffractive waveguide designs, and mode-specific polarization control. This framework was experimentally validated in the terahertz spectrum to selectively pass certain spatial modes while rejecting others. Without the need for material dispersion engineering diffractive waveguides can be scaled to operate at different wavelengths, including visible and infrared spectrum, covering potential applications in, e.g., telecommunications, imaging, sensing and spectroscopy.

Applied optics↗

Particle resonances in toroidal fusion devices

Resonances of high energy particles in magnetic confinement devices due to electromagnetic instabilities can strongly modify the distribution, leading to a reduction in fusion power and even discharge termination and particle loss to the device walls through avalanche. The existence of a mode particle resonance depends on properties of the equilibrium, particle trajectories, and perturbation mode harmonic content. Resonance location is a function of particle energy and equilibrium field line helicity. Different methods for finding resonance location and energy dependence are developed. The properties of resonances are discussed using examples from magnetic fusion devices. Here, we show that if mode resonances exist at low particle energy, they very likely also exist at high energy, thus modifying high energy beam particles and fusion products. It is possible for a resonance to appear due to mode induced orbit helicity modification when it is forbidden at low mode amplitude.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Cooling and instabilities in colliding radiative flows with toroidal magnetic fields

ABSTRACT We report on the results of a simulation-based study of colliding magnetized plasma flows. Our set-up mimics pulsed power laboratory astrophysical experiments but, with an appropriate frame change, is relevant to astrophysical jets with internal velocity variations. We track the evolution of the interaction region where the two flows collide. Cooling via radiative losses is included in the calculation. We systematically vary plasma beta (βm) in the flows, the strength of the cooling (Λ0), and the exponent (α) of temperature dependence of the cooling function. We find that for strong magnetic fields a counter-propagating jet called a ‘spine’ is driven by pressure from shocked toroidal fields. The spines eventually become unstable and break apart. We demonstrate how formation and evolution of the spines depend on initial flow parameters and provide a simple analytical model that captures the basic features of the flow.

79 ASTRONOMY AND ASTROPHYSICS↗

Angle-resolved pair photoemission theory for correlated electrons

Here in this paper we consider the possibility and conditions for pair photoemission whereby two incident photons emit pairs of electrons from a candidate material as a novel method to measure and visualize electronic correlations. As opposed to double photoemission - where a single photon precipitates the ejection of a pair electrons via a subsequent electron energy loss scattering process - we show that pair photoemission need not be limited to interference between initial photoelectrons and valence electrons, and moreover, can occur without the energy penalty of two work functions. This enables detection of pairs of electrons at high energy resolution that may be correlated in the same quantum many-body states.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

A Novel Anatomic Reconstruction for Posterior Tibialis Tendon in Treatment of Flexible Adult‐Acquired Flatfoot Deformity

Objective To present a novel approach for the anatomic reconstruction of the posterior tibialis tendon (PTT) in restoring plantar insertions and evaluate its efficiency in treating flexible adult‐acquired flatfoot deformity (AAFD) caused by PTT dysfunction. Methods For AAFD treatment, a novel PTT reconstruction method was presented. The current study involved 16 patients, including three men, and 13 women, from August 2017 to July 2019. The mean age was 43.2 ± 15.1 years (21–64 years). The innovative PTT repair method was used on all patients. The treatment involved performing a traditional Flexor Digitorum Longus (FDL) transfer in the navicular tuberosity and suturing the plantar insertions to FDL as tension was applied to tighten the plantar structures of the foot. The results were retrospectively analyzed. The clinical outcome was assessed using the pain visual analogue scale (VAS), the satisfaction VAS, and the American Orthopedic Foot and Ankle Society ankle–hindfoot scale (AOFAS‐AH). Isokinetic testing was performed using a dynamometer at 60°/s and 120°/s for inversion/eversion and plantarflexion/dorsiflexion, respectively, to determine the mean peak torque. Radiographic measurements were employed to assess the outcomes. Results Bone surgeries combined with the modified anatomic PTT reconstruction were performed on patients with medializing calcaneal osteotomy in 12 (75%) patients and subtalar joint fusion in four (25%) patients. The branch linking to the plantar insertions was detected in every case, with an average width of 3.5 ± 0.8 mm (3.1–4.3 mm). All patients were followed up for the mean of 16.8 ± 1.8 months (range, 15–20 months). The average postoperative functional scores, including pain VAS, satisfaction VAS, total AOFAS‐AH, and all AOFAS‐AH sub‐scales, steadily improved during the follow‐up. In the last follow‐up, isokinetic testing revealed no loss of plantarflexion strength ( p = 0.350 and 0.098) and significant improvement in the inversion strength ( p = 0.007 and 0.008) in the operated ankles at 60°/s and 120°/s. Radiographic outcomes, particularly the talar head uncovering, improved significantly after more than a year ( p < 0.001 for all). Conclusions The novel technique for PTT reconstruction in restoring the plantar insertions serves as an effective procedure in treating AAFD caused by PTT dysfunction in terms of delivering a consistent improvement in ankle inversion strength, medial longitudinal arch restoring, and satisfactory clinical outcomes.

Hu, Yong↗

Clinical effects of 3D printing-assisted posterolateral incision in the treatment of ankle fractures involving the posterior malleolus

Objective To explore the clinical outcomes of a 3D printing-assisted posterolateral approach for the treatment of ankle fractures involving the posterior malleolus. Methods A total of 51 patients with ankle fractures involving the posterior malleolus admitted to our hospital from January 2018 to December 2019 were selected. The patients were divided into 3D printing group (28 cases) and control group (23 cases). 3D printing was performed for ankle fractures, followed by printing of a solid model and simulation of the operation on the 3D model. The operation was then performed according to the preoperative plan, including open reduction and internal fixation via the posterolateral approach with the patient in the prone position. Routine x-ray and CT examinations of the ankle joint were performed, and ankle function was evaluated using the American Foot and Ankle Surgery Association (AOFAS) ankle-hindfoot score. Results All patients underwent x-ray and CT examinations. All fractures healed clinically, without loss of reduction or failure of internal fixation. Good clinical effects were achieved in both groups of patients. The operation time, intraoperative blood loss and intraoperative fluoroscopy frequency in the 3D printing group were significantly less than those in the control group ( p < 0.05). There was no significant difference between the two groups in the anatomical reduction rate of fractures or the incidence of surgical complications ( p > 0.05). Conclusion The 3D printing-assisted posterolateral approach is effective in the treatment of ankle fractures involving the posterior malleolus. The approach can be well planned before the operation, is simple to perform, yields good fracture reduction and fixation, and has good prospects for clinical application.

Zheng, Hongming↗

Muon Time-of-Flight studies for cosmic background rejection in the Short Baseline Near Detector

The Short-Baseline Neutrino (SBN) program at Fermilab is a cutting-edge project in experimental neutrino physics. One of its main goals is to systematically investigate the possible existence of eV-scale sterile neutrinos. This phenomenon has been hypothesized to explain some anomalies found in short-range experiments and, if confirmed, would imply a substantial extension of the Standard Model. SBN also offers an important opportunity to deepen the understanding of neutrino-nucleus interactions in the GeV energy range, through the use of Liquid Argon Time Projection Chambers (LArTPC) detectors, a fundamental technology also for the future DUNE experiment. The SBN experimental infrastructure consists of three detectors aligned along the Booster Neutrino Beamline at Fermilab. Among them, the detector located closest to the neutrino source, SBND (Short-Baseline Near Detector), positioned approximately 110 meters from the target, plays a key role in directly characterizing the initial neutrino flux. This allows for a direct comparison with the measurements from the far detector, ICARUS, located about 600 meters from the source, in order to search for potential signs of anomalous neutrino oscillations. My master's thesis focuses on the commissioning and characterization activities of the SBND detector, with particular reference to the Cosmic Ray Tagger (CRT). The CRT is a subsystem for identifying and rejecting events produced by cosmic rays, which constitute the main source of background for surface experiments like SBND. The activity began with the commissioning of the final components of the detector, as well as their validation to verify their correct functioning and signal acquisition. A central part of my work involved studying the veto efficiency of the CRT system, analyzing the rate of cosmic ray-induced events to quantify any loss of neutrino-induced events caused by cosmic background. This allowed for a more precise evaluation of the systematic impact of the CRT on the useful physics sample. A further phase of my analysis involved an in-depth study of the temporal correlation between the CRT signals and those acquired by the LArTPC's internal photodetector system, consisting of photomultiplier tubes and X-ARAPUCA devices. The objective is to explore the possibility of using combined temporal information as an additional criterion for discriminating between cosmic signals and signals genuinely due to neutrino interaction. Preliminary results indicate the presence of characteristic temporal signatures that could be exploited to improve event selection and increase the purity of the neutrino-induced sample. These methodologies will certainly contribute to the optimization of SBND analysis strategies and, more generally, to a better understanding of background mechanisms in next-generation LArTPC experiments.

Corallo, Annalea [Ferrara U.]↗

Comparison of inclusive and photon-tagged jet suppression in 5.02 TeV Pb+Pb collisions with ATLAS

Parton energy loss in the quark–gluon plasma (QGP) is studied with a measurement of photon-tagged jet production in 1.7 nb –1 of Pb+Pb data and 260 pb –1 of pp data, both at $\sqrt{^S{\text{NN}}}$ = 5.02 TeV, with the ATLAS detector. The process $pp$ → γ +jet+X and its analogue in Pb+Pb collisions is measured in events containing an isolated photon with transverse momentum ($p_{\text{T}}$) above 50 GeV and reported as a function of jet $p_{\text{T}}$. This selection results in a sample of jets with a steeply falling $p_{\text{T}}$ distribution that are mostly initiated by the showering of quarks. The $pp$ and Pb+Pb measurements are used to report the nuclear modification factor, $R_{\text{AA}}$, and the fractional energy loss, $S_{\text{loss}}$, for photon-tagged jets. In addition, the results are compared with the analogous ones for inclusive jets, which have a significantly smaller quark-initiated fraction. The $R_{\text{AA}}$ and $S_{\text{loss}}$ values are found to be significantly different between those for photon-tagged jets and inclusive jets, demonstrating that energy loss in the QGP is sensitive to the colour-charge of the initiating parton. Finally, the results are also compared with a variety of theoretical models of colour-charge-dependent energy loss.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Operation and Control of Electric Vehicle Charger with Enhanced Dynamic Performance Under Non-Ideal Grid Voltage Condition

This paper presents a three-phase electric vehicle charger connected to the grid, featuring multiple boost converters on the DC side, specifically designed to ensure smooth, oscillation-free power transfer during unsymmetrical voltage sags. Precise control mechanisms are implemented on the boost converter side to regulate both voltage and current on the electric vehicle side, thereby maintaining optimal charging conditions. The control architecture for both the grid-connected and boost converter components is based on the Lyapunov energy function, which is employed to achieve superior dynamic performance and stability. The system's robustness and reliability are demonstrated through its ability to maintain stable operation and efficient power transfer despite fluctuations in grid conditions. Furthermore, the implementation of Lyapunov-based control ensures rapid response and minimal energy loss, enhancing the overall efficiency of the system. To validate the effectiveness of this approach, a comprehensive model of the system was developed and tested using MATLAB/Simulink, with detailed computer simulations conducted across various significant case studies.

DC-DC boost converter↗

The RNA-binding protein Modulo promotes neural stem cell maintenance in Drosophila

A small population of stem cells in the developing Drosophila central nervous system generates the large number of different cell types that make up the adult brain. To achieve this, these neural stem cells (neuroblasts, NBs) divide asymmetrically to produce non-identical daughter cells. The balance between stem cell self-renewal and neural differentiation is regulated by various cellular machinery, including transcription factors, chromatin remodelers, and RNA-binding proteins. The list of these components remains incomplete, and the mechanisms regulating their function are not fully understood, however. Here, we identify a role for the RNA-binding protein Modulo (Mod; nucleolin in humans) in NB maintenance. We employ transcriptomic analyses to identify RNA targets of Mod and assess changes in global gene expression following its knockdown, results of which suggest a link with notable proneural genes and those essential for neurogenesis. Mod is expressed in larval brains and its loss leads to a significant decrease in the number of central brain NBs. Stem cells that remain lack expression of key NB identity factors and exhibit cell proliferation defects. Mechanistically, our analysis suggests these deficiencies arise at least in part from altered cell cycle progression, with a proportion of NBs arresting prior to mitosis. Overall, our data show that Mod function is essential for neural stem cell maintenance during neurogenesis.

Parra, Amalia S.↗

Li 8 MnO 6 : A Novel Cathode Material with Only Anionic Redox

In Li-excess transition-metal-oxide cathode materials, anionic oxygen redox can offer high capacity and high voltages, although peroxo and superoxo species may cause oxygen loss, poor cycling performance, and capacity fading. Previous work showed that undesirable formation of peroxide and superoxide bonds is controlled to some extent by Mn substitution, and the present work uses density functional calculations to examine the reasons for this by studying the anionic redox mechanism Li 8 MnO 6 . This material is obtained by substituting Mn for Sn in Li 8 SnO 6 or for Zr in Li 8 ZrO 6 , and we also compare to previous work on those materials. The calculations predict that Li 8 MnO 6 is stable at room temperature (with a band gap of 3.19 eV as calculated HSE06 and 1.82 eV as calculated with the less reliable with PBE+U), and they elucidate the chemical and structural effects involved in the inhibition of oxygen release in this cathode. Throughout the whole delithiation process, only O 2- ions are oxidized. The directional Mn-O bonds formed from unfilled 3d orbitals effectively inhibit the formation of O-O bonds, and the layered structure is maintained even after removing 3 Li per Li 8 MnO 6 formula unit. The calculated average voltage for removal of 3 Li is 3.69 V by HSE06, and the corresponding capacity is 389 mAh/g. The high voltage of oxygen anionic redox and the high capacity result in a high energy density of 1436 Wh/kg. The Li-ion diffusion barrier for the dominant interlayer diffusion path along the c-axis is 0.57 eV by PBE+U. Finally, these results help us to understand the oxygen redox mechanism in a new lithium-rich Li 8 MnO 6 cathode material and contribute to the design of high-energy-density lithium-ion-battery cathode materials with favorable electrochemical properties based on anionic oxygen redox.

Li8MnO6↗

Rapidly convergent quantum Monte Carlo using a Chebyshev projector

The multireference coupled-cluster Monte Carlo (MR-CCMC) algorithm is a determinant-based quantum Monte Carlo (QMC) algorithm that is conceptually similar to Full Configuration Interaction QMC (FCIQMC). It has been shown to offer a balanced treatment of both static and dynamic correlation while retaining polynomial scaling, although application to large systems with significant strong correlation remained impractical. In this paper, we document recent algorithmic advances that enable rapid convergence and a more black-box approach to the multireference problem. These include a logarithmically scaling metric-tree-based excitation acceptance algorithm to search for determinants connected to the reference space at the desired excitation level and a symmetry-screening procedure for the reference space. We show that, for moderately sized reference spaces, the new search algorithm brings about an approximately 8-fold acceleration of one MR-CCMC iteration, while the symmetry screening procedure reduces the number of active reference space determinants with essentially no loss of accuracy. We also introduce a stochastic implementation of an approximate wall projector, which is the infinite imaginary time limit of the exponential projector, using a truncated expansion of the wall function in Chebyshev polynomials. Notably, this wall-Chebyshev projector can be used to accelerate any projector-based QMC algorithm. We show that it requires significantly fewer applications of the Hamiltonian to achieve the same statistical convergence. We benchmark these acceleration methods on the beryllium and carbon dimers, using initiator FCIQMC and MR-CCMC with basis sets up to cc-pVQZ quality.

Zhao, Zijun↗

Examination of decay heat measurements and their relevance for understanding the origin of the reactor antineutrino anomaly

Measurements of the decay energy released as a function of time following the thermal neutron induced fission of 235 U and 239,241 Pu were performed in the 1970s at Oak Ridge National Laboratory with the purpose of quantifying possible loss of coolant accident scenarios. The derivative of this decay energy with respect to time, known in technical parlance as decay heat, is mainly composed of two terms, that of the electrons produced together with antineutrinos in the $β$-minus decay of the neutron-rich fission products, and that of the $γ$ rays produced in the subsequent decay of excited nuclear levels. In this work we study if this extensive set of decay energy measurements can be used to assess the reactor antineutrino anomaly, that is, the approximately 5% deficit of electron antineutrinos produced by nuclear reactors, first deduced by Mention and collaborators in 2011, and observed by the major reactor antineutrino experiments since. Furthermore, with the assistance of nuclear databases, we are able to obtain the ratio of electron spectra under equilibrium conditions for 235 U to 239 Pu, in better agreement with the lower trend recently reported by Kopeikin and collaborators, as well as those for 235 U to 241 Pu and 241 Pu to 239 Pu, which do not agree well with those measured at the Institut Laue-Langevin in the 1980s. We conclude that a new experimental campaign is needed to measure the electron spectra utilizing a high resolution and signal-to-noise-ratio electron spectrometer and a highly precise fission normalization procedure.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

2023 American Society for Mass Spectrometry (ASMS) 71st Annual Conference on Mass Spectrometry and Allied Topics

Introduction (120 words max) Understanding metal-cluster chemistry occuring at solvent boundaries in the aqueous and organic phases has applications in environments from cellular processes to nuclear fuel reprocessing. Transport of metal ions at the boundaries from aqueous to organic phases involves forming a metal-ligand complex, and wherever the initial metal coordination environment is significantly different from the final one, the metal transitions through a series of transient species in passing from one phase to another. Here an investigation of the role of coordination in the chemistry of the transient species using gas-phase measurements that are free of solvent effects to better understand the binding of complexes of metals with triphenylphosphine chalcogenide ligands, examining metal-ligand homo- and hetero-dimers to better understand transient species. Methods (120 word max) Mass spectrometry and collision induced dissociation (CID) experiments were performed with a Bruker (Billerica, MA, USA) micrOTOF-Q II quadrupole time-of-flight mass spectrometer (QTOF) and Bruker amaZon speed ETD (ion trap). High resolution/high mass accuracy spectra were generated using the QTOF. External calibration was performed with Agilent (Santa Clara, CA, USA) ESI-L Low Concentration tuning mix. Both mass spectrometers were equipped with either the electrospray ionization source or nanospray sources. Metal samples were prepared between 40 – 60 uM of the metal-ligand complex in 25% water and 75% acetonitrile. Metal-ion clusters were isolated and subjected to collision induced dissociation. Density functional theory calculations were performed. Preliminary Data or Plenary Speakers Abstract (300 words max) Metal ion clusters with triphenylphosphine chalcogenide ligands were observed for group I metals with triphenylphosphine chalcogenide samples in the mass spectrum upon electrospray ionization. For each metal ligand complex of interest, the parent ion was isolated and collision induced dissociation fragmentation spectra were acquired. We observed clusters of group I metal with triphenylphosphine oxide, triphenyl phosphine sulfide, and triphenylphosphine selenide, with homodimers and heterodimer formation. In samples where the ligands were mixed, we observed mixed sodium ligand clusters at varying amounts. These mixed ligand clusters were fragmented. Metal clusters of mixed ligand dimers containing triphenylphosphine oxide showed preferential loss of the other ligand, either triphenylphosphine sulfide or triphenyl selenide. In samples with mixed triphenylphosphine sulfide and triphenylphosphine selenium ligands, sodium bound similarly between the ligands, and losses were more evenly split, showing loss ratio upon CID with losses of triphenylphosphine sulfide:triphenylphosphine selenide 43:57 ratio observed on CID. These results suggest that the oxide binds significantly more strongly than either the selenium or sulfur triphenylphosphine ligand, and the sulfur and selenium ligands are more evenly bound. Calculations were performed using density functional theory to calculate likely structures and bond energies between the group I metal and the ligands. Novel Aspect Novel analysis of sodium bound dimers with chalcogenide triphenylphosphine ligands were investigated using mass spectrometry and theoretical calculations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗