Low State Research Articles

Exploring the photochemistry of OAlOH: Photodissociation pathways and electronic spectra.

This study was focused on the photochemistry of OAlOH and three possible pathways, which were studied with high-level multireference configuration interaction abinitio calculations. We computed cuts of the six-dimensional potential energy surfaces for the ground, the lowest singlet and triplet excited states, and probed the photodissociation mechanisms and the stabilities. The OAlOH electronic spectrum, with an energy reaching 7.15eV, contained four prominent peaks. Photodissociation to AlO, OH, and AlOH constituted a plausible mechanism within the deep-UV range (λ = 250.4nm). Our data indicated the photostability of OAlOH in the near-UV‒Vis region, so detection with laser-induced fluorescence is possible. Fluorescence and phosphorescence may occur upon excitation at 363.5nm. The roles of OAlOH in the photochemical reactions of Al-bearing molecules in the upper atmosphere and VY Canis Majoris are discussed.

Chelate Complexes of 3d Transition Metal Ions─A Challenge for Electronic-Structure Methods?

Different electronic-structure methods were assessed for their ability to predict two important properties of the industrially relevant chelating agent nitrilotriacetic acid (NTA): its selectivity with respect to six different first-row transition metal ions and the spin-state energetics of its complex with Fe(III). The investigated methods encompassed density functional theory (DFT), the random phase approximation (RPA), coupled cluster (CC) theory, and the auxiliary-field quantum Monte Carlo (AFQMC) method, as well as the complete active space self-consistent field (CASSCF) method and the respective on-top methods: second-order N-electron valence state perturbation theory (NEVPT2) and multiconfiguration pair-density functional theory (MC-PDFT). Different strategies for selecting active spaces were explored, and the density matrix renormalization group (DMRG) approach was used to solve the largest active spaces. Despite somewhat ambiguous multi-reference diagnostics, most methods gave relatively good agreement with experimental data for the chemical reactions connected to the selectivity, which only involved transition-metal complexes in their high-spin state. CC methods yielded the highest accuracy followed by range-separated DFT and AFQMC. We discussed in detail that even higher accuracies can be obtained with NEVPT2, under the prerequisite that consistent active spaces along the entire chemical reaction can be selected, which was not the case for reactions involving Fe(III). A bigger challenge for electronic-structure methods was the prediction of the spin-state energetics, which additionally involved lower spin states that exhibited larger multi-reference diagnostics. Conceptually different, typically accurate methods ranging from CC theory via DMRG-NEVPT2 in combination with large active spaces to AFQMC agreed well that the high-spin state is energetically significantly favored over the other spin states. This was in contrast to most DFT functionals and RPA which yielded a smaller stabilization and some common DFT functionals and MC-PDFT even predicting the low-spin state to be energetically most favorable.

Loading or Unloading? This Is the Question! A Multi-Season Study in Professional Football Players

This study examined the impact of training load periodization on neuromuscular readiness in elite football players using the Locomotor Efficiency Index (LEI) as a measure of performance optimization. Throughout the 2021/22 and 2022/23 seasons, 106 elite male players (age: 19.5 ± 3.9 years) from an Italian professional football club were monitored using Global Positioning Systems (GPS) external load data. The LEI was derived from a machine learning model, specifically random forest regression, which compared predicted and actual PlayerLoad™ values to evaluate neuromuscular efficiency. Players were categorized by weekly LEI into three readiness states: bad, normal, and good. Analysis focused on the variation in weekly LEI relative to weekly load percentage variation (large decrease, moderate decrease, no variation, moderate increase, large increase), which included total distance, high-speed distance (above 25.2 km/h), and mechanical load, defined as the sum of accelerations and decelerations. Statistical analysis showed significant differences only with variations in total distance and mechanical load. Specifically, reducing weekly loads improved LEI in players in lower readiness states, while maintaining or slightly increasing loads promoted optimal readiness. This approach enables coaches to tailor training prescriptions more effectively, optimizing workload and recovery to sustain player performance throughout a demanding season.

BaCoO2 with Tetrahedral Cobalt Coordination: The Missing Element to Understand Energy Storage and Conversion Applications in BaCoO3-δ-Based Materials.

Barium-cobaltate-based perovskite (BaCoO3-δ) and barium-cobaltate-based nanocomposites have been intensively studied in energy storage and conversion devices mainly due to flexible oxygen stoichiometry and tunable nonprecious transition metal oxidation states. Although a rich and complex family of structural polymorphs has already been reported for these perovskites in the literature, the potential structural evolution that may occur during the oxygen reduction reaction and the oxygen evolution reaction has not been investigated so far. In this study, we synthesized and characterized the lowest Co-oxidation state possible in the compound, BaCoO2, which exhibits a quartz-derived, trigonal structure with a helicoidally corner-sharing, CoO4-tetrahedral-framework as already proposed by Spitsbergen et al. Oxygen can reversibly be inserted in such a crystal structure to form BaCoO3-δ, i.e., with 0 ≤ δ ≤ 1, based on the results of an in situ coupled thermogravimetric - neutron diffraction study and which presents therefore giant oxygen capacity storage due to the extreme tunability of the electronic configuration of the cobalt cations which defines the fundamental origins of the materials performance. The reversible conversion of BaCoO2 to BaCoO3-δ associated with a similar electronic conductivity above 900 K permits to clarify the high potential of BaCoO3-δ-based energy storage and conversion devices.

Superconformal indices and localization in N = 2B quantum mechanics

Superconformal ‘type B’ quantum mechanical sigma models arise in a variety of interesting contexts, such as the description of D-brane bound states in an AdS2 decoupling limit. Focusing on N = 2B models, we study superconformal indices which count short multiplets and provide an alternative to the standard Witten index, as the latter suffers from infrared issues. We show that the basic index receives contributions from lowest Landau level states in an effective magnetic field and that, due to the noncompactness of the target space, it is typically divergent. Fortunately, the models of interest possess an additional target space isometry which allows for the definition of a well-behaved refined index. We compute this index using localization of the functional integral and find that the result agrees with a naive application of the Atiyah-Bott fixed point formula outside of it’s starting assumptions. In the simplest examples, this formula can also be directly verified by explicitly computing the short multiplet spectrum.

Electric dipole polarizability of low-lying excited states in atomic nuclei

Abstract New equations for the electric dipole polarizability αE1 of low-lying excited states in atomic nuclei — and the related (–2) moment of the total photo-absorption cross section, σ–2 — are inferred in terms of electric dipole and quadrupole matrix elements. These equations are valid for arbitrary angular momenta of the initial/ground and final/excited states and have been exploited in fully converged 1h̄ω shell-model calculations of selected p- and sd-shell
nuclei that consider configuration mixing; advancing previous knowledge from 17O to 36Ar, where thousands of electric dipole matrix elements are computed from isovector excitations which include the giant dipole resonance region. Our results are in reasonable agreement with previous shell-model calculations and follow — except for 6,7 Li and 17,18 O — Migdal’s global trend provided by the combination of the hydrodynamic model and second-order non-degenerate perturbation theory. Discrepancies in 6,7Li and 17O arise as a result of the presence of α-cluster configurations in odd-mass nuclei, whereas the disagreement in 18O comes from the mixing of intruder states, which is lacking in the shell-model interactions. More advanced ab initio calculations of the dipole polarizability for low-lying excited states covering all the isovector states within the giant dipole resonance region are missing and could be very valuable to benchmark the results presented here and shed further light on how atomic nuclei polarize away from the ground state

The Effect of Aromatherapy on Anxiety and Pain in Patients Undergoing Oculoplastic Surgery.

To determine the effect of aromatherapy on postoperative anxiety and pain in patients undergoing oculoplastic surgery. A randomized controlled study of 60 patients who underwent monitored anesthesia care sedation for oculoplastic procedures from August 2018 to November 2020. Patients were randomized to an aromatherapy (n = 32) or placebo (n = 28) condition. Anxiety was measured with State-Trait Anxiety Inventory and visual analog scale for anxiety. Pain was measured with a visual analog scale for pain. Compared with control patients, aromatherapy patients had significantly lower postoperative State-Trait Anxiety Inventory state anxiety (24.1 vs. 29.1; p = 0.05) and visual analog scale pain scores (1.9 vs. 3.2; p = 0.05). Aromatherapy patients also had shorter stays in the postanesthesia care unit than control patients (57.7 vs. 79.4 minutes; p = 0.03). Patients who received aromatherapy reported lower postoperative anxiety and pain. Aromatherapy may be a useful adjuvant analgesic and/or anxiolytic for patients undergoing oculoplastic procedures with monitored anesthesia care sedation.

An inverted singlet-triplet excited state in a pentaazaphenalene derivative (5AP-N(C12)2)

Abstract The characteristic of inverted singlet-triplet excited states (iST), in which the lowest singlet excited state (S1) is lower than the lowest triplet state (T1) in energy, was observed in a dialkylamine-substituted pentaazaphenalene derivative, 5AP-N(C12)2. The transient PL measurements showed that the reverse intersystem crossing has virtually zero activation energy, whereas the intersystem crossing proceeded by a thermal activation process. T1 was located energetically above S1 with the negative energy gap between S1 and T1 (ΔE ST) of −37 meV. Fluorescence and phosphorescence spectra also confirmed the negative ΔE ST of −46 – −32 meV.

Millimeter-wave and high-resolution infrared spectroscopy of the low-lying vibrational states of pyridazine isotopologues.

The gas-phase rotational spectrum from 8 to 750GHz and the high-resolution infrared (IR) spectrum of pyridazine (o-C4H4N2) have been analyzed for the ground and four lowest-energy vibrationally excited states. A combined global fit of the rotational and IR data has been obtained using a sextic, centrifugally distorted-rotor Hamiltonian with Coriolis coupling between appropriate states. Coriolis coupling has been addressed in the two lowest-energy coupled dyads (ν16, ν13 and ν24, ν9). Utilizing the Coriolis coupling between the vibrational states of each dyad and the analysis of the IR spectrum for ν16 and ν9, we have determined precise band origins for each of these fundamental states: ν16 (B1) = 361.213 292 7 (17) cm-1, ν13 (A2) = 361.284 082 4 (17) cm-1, ν24 (B2) = 618.969 096 (26) cm-1, and ν9 (A1) = 664.723 378 4 (27) cm-1. Notably, the energy separation in the ν16-ν13 Coriolis-coupled dyad is one of the smallest spectroscopically measured energy separations between vibrational states: 2122.222 (72) MHz or 0.070 789 7 (24) cm-1. Despite ν13 being IR inactive and ν24 having an impractically low-intensity IR intensity, the band origins of all four vibrational states were measured, showcasing the power of combining the data provided by millimeter-wave and high-resolution IR spectra. Additionally, the spectra of pyridazine-dx isotopologues generated for a previous semi-experimental equilibrium structure (reSE) determination allowed us to analyze the two lowest-energy vibrational states of pyridazine for all nine pyridazine-dx isotopologues. Coriolis-coupling terms have been measured for analogous vibrational states across seven isotopologues, both enabling their comparison and providing a new benchmark for computational chemistry.

Lifetime measurements in the yrast band of 187Hg

Lifetimes of excited nuclear states in 187Hg have been measured using the 159Tb (32S, p3n)187Hg reaction at a beam energy of 154 MeV at the Inter University Accelerator Center, Delhi. In the experiment, the lifetimes of the five lowest yrast states have been determined using the recoil distance Doppler-shift (RDM) method. The extracted transition quadrupole moments show a sharp increase with increasing level spin, indicating a major shape transition happening in this nucleus. For a better insight into the predicted shape coexistence picture in 187Hg nucleus, the experimental results are compared with the results of the total Routhian surface calculations. The results indicate the shifting of deformed structures from weakly prolate at low-spins to strongly prolate at high spins in 187Hg nucleus.

Quasi-degenerate extension of local N-electron valence state perturbation theory with pair-natural orbital method based on localized virtual molecular orbitals.

Chemical phenomena involving near-degenerate electronic states, such as conical intersections or avoided crossing, can be properly described using quasi-degenerate perturbation theory. This study proposed a highly scalable quasi-degenerate second-order N-electron valence state perturbation theory (QD-NEVPT2) using the local pair-natural orbital (PNO) method. Our recent study showed an efficient implementation of the PNO-based state-specific NEVPT2 method using orthonormal localized virtual molecular orbitals (LVMOs) as an intermediate local basis. This study derived the state-coupling (or off-diagonal) terms to implement QD-NEVPT2 in an alternative manner to enhance efficiency based on the internally contracted basis and PNO overlap matrices between different references. To facilitate further acceleration, a local resolution-of-the-identity (RI) three-index integral generation algorithm was developed using LMOs and LVMOs. Although the NEVPT2 theory is considered to be less susceptible to the intruder-state problem (ISP), this study revealed that it can easily suffer from ISP when calculating high-lying excited states. We ameliorated this instability using the imaginary level shift technique. The PNO-QD-NEVPT2 calculations were performed on small organic molecules for the 30 lowest-lying states, as well as photoisomerization involving the conical intersection of 1,1-dimethyldibenzo[b,f] silepin with a cis-stilbene skeleton. These calculations revealed that the PNO-QD-NEVPT2 method yielded negligible errors compared to the canonical QD-NEVPT2 results. Furthermore, we tested its applicability to a large photoisomerization system using the green fluorescent protein model and the ten-state calculation of the large transition metal complex, showcasing that off-diagonal elements can be evaluated at a relatively low cost.

Theoretical study on the mechanism of alcohol photooxidation on Nb2O5 surface.

Theoretical modeling of the solid-state photocatalysis is one of the important issues as various useful photocatalysts have been developed to date. In this work, we investigated the mechanism of the alcohol photooxidation on niobium oxide (Nb2O5) which was experimentally developed, using the density functional theory (DFT)/time-dependent (TD)DFT calculations based on the cluster model. The alcohol adsorption and the first hydrogen transfer from hydroxy group to surface occur in the ground state, while the second hydrogen transfer from CH proceeds in the excited states during the photoirradiation of UV or visible light. The spin crossing was identified and the low-lying triplet states were solved for the reaction pathway. The photoabsorption in the visible light region was characterized as the charge transfer transition from O 2p of alcohol to Nb 4d of the Nb2O5 surface. The spin density and the natural population analysis indicated the generation of spin density in the moiety of carbonyl compound and its dissipation to the interface of the surface, which partly explains the electron paramagnetic resonance measurement. It was confirmed that the rate determining step is the desorption of carbonyl compound and water molecule in agreement with the experimental rate equation analysis. The present findings with the theoretical modeling will provide useful information for the further studies of the solid-state photocatalysis.

Bound states from the spectral Bethe-Salpeter equation

We compute the bound state properties of three-dimensional scalar ϕ4 theory in the broken phase. To this end, we extend the recently developed technique of spectral Dyson-Schwinger equations to solve the Bethe-Salpeter equation and determine the bound state spectrum. We employ consistent truncations for the two-, three- and four-point functions of the theory that recover the scaling properties in the infinite coupling limit. Our result for the mass of the lowest-lying bound state in this limit agrees very well with lattice determinations. Published by the American Physical Society 2024

An Intruder-Free Fock Space Coupled-Cluster Study of the Potential Energy Curves of LiMg+ within the (2,0) Sector.

The potential energy curves (PECs) and spectroscopic constants of the ground and excited states of a LiMg+ molecular cation were investigated. We obtained accurate results for the fifteen lowest-lying states of the LiMg+ cation using the Intermediate Hamiltonian Fock Space Multireference Coupled Cluster (IH-FS-CC) method applied to the (2,0) sector. Relativistic corrections were accounted for using the third-order Douglas-Kroll method. In each instance, smooth PECs were successfully computed across the entire range of interatomic distances from equilibrium to the dissociation limit. The results are in good accordance with previous studies of this molecular cation. Notably, this study marks the first application of IH-FS-CC in investigating a mixed alkali and alkaline earth molecular cation, proving its usability in determining accurate PECs of such diatomics and their spectroscopic constants.

Effects of Residual Tensor and Pairing Forces on the Gamow-Teller states in Magic Nuclei, 48Ca, 90Zr, 132Sn, and 208Pb

Abstract We investigate the effects of residual tensor force (TF) and pairing force on the Gamow-Teller (GT) transitions in four magic nuclei, 48Ca, 90Zr, 132Sn and 208Pb. The TF is taken into account by using the Brückner G-matrix theory with the charge-dependent (CD) Bonn potential as the residual interaction of charge-exchange quasiparticle random phase approximation (QRPA). We found that particle-particle (p − p) tensor interaction does not affect the GT transitions because of the closed shell nature in the nuclei, but repulsive particle-hole (p − h) residual interaction for the p − h configuration of spin-orbit partners dominates the high-lying giant GT states for all of the nuclei. It is also shown that appreciable GT strengths are shifted to lower energy region by the attractive p − h TF for the same jπ = jν configuration, and produce the low-lying GT peak about 2.5 MeV in 48Ca. Simultaneously, in 90Zr and 132Sn, the low-energy GT strength appears as a lower energy shoulder near the main GT peak. On the other hand, the shift of the low-lying GT state is not seen clearly for 208Pb because of the strong spin-orbit splitting of high j orbits, which dominates the GT strength.

Dominant nucleon-pair configurations in low-lying states of deformed nuclei

Dominant nucleon-pair configurations in low-lying states of deformed nuclei

Study the structure of the low-lying states of 206Po

The nucleus 206Po was studied in the two proton transfer reaction 204Pb(16O,14C)206Po and the lifetime of the first excited 2+ state was determined by utilizing the Recoil Distance Doppler Shift method. The experimental results are compared with shell-model calculations based on different effective interactions. The calculations qualitatively reproduced the experimentally observed B(E2;21+→01+) value, suggesting that the 21+ state of 206Po exhibits a collective nature. However, the employed effective interactions revealed some limitations, particularly in their description of the 41,2+ states. These results emphasize the importance of understanding the properties of low-lying states, especially their evolution from single-particle dynamics to collective modes, in evaluating various effective nuclear interactions.

Ab initio spectroscopy and thermochemistry of the platinum hydride ions, PtH+ and PtH.

Rovibrational levels of low-lying electronic states of the gas-phase, diatomic molecules, PtH+ and PtH-, are computed on potential-energy functions obtained by using a hybrid spin-orbit configuration-interaction procedure. PtH- has a well-separated Σ0++1 ground state, while the first two electronic states of PtH+ (Σ0++1 and 3Δ3) are nearly degenerate. Combining the experimental photoelectron (PE) spectra of PtH- with theoretical photodetachment spectroscopy leads to an improved value for the electron affinity of PtH, EA(PtH) = (1.617 ± 0.015) eV. When PtH- is a product of photodissociation of PtHCO2-, its PE spectrum is broad because of rotational excitation. Temperature-dependent thermodynamic functions and thermochemistry of dissociation are computed from the theoretical energy levels. Previously published energetic quantities for PtH+ and PtH- are revised. The ground 1Σ+ term of PtH+ is not well described using single-reference theory.

Multistate Dynamics and Kinetics of CO2 Activation by Ta+ in the Gas Phase: Insights into Single-Atom Catalysis.

The activation of carbon dioxide (CO2) by a transition-metal cation in the gas phase is a unique model system for understanding single-atom catalysis. The mechanism of such reactions is often attributed to a "two-state reactivity" model in which the high-energy barrier of a spin state correlating with ground-state reactants is avoided by intersystem crossing (ISC) to a different spin state with a lower barrier. However, such a "spin-forbidden" mechanism, along with the corresponding dynamics, has seldom been rigorously examined theoretically, due to the lack of global potential energy surfaces (PESs). In this work, we report full-dimensional PESs of the lowest-lying quintet, triplet, and singlet states of the TaCO2+ system, machine-learned from first-principles data. These PESs and the corresponding spin-orbit couplings enable us to provide an extensive theoretical characterization of the dynamics and kinetics of the reaction between the tantalum cation (Ta+) and CO2, which have recently been investigated experimentally at high collision energies using crossed beams and velocity map imaging, as well as at thermal energies using a selected-ion flow tube apparatus. The multistate quasi-classical trajectory simulations with surface hopping reproduce most of the measured product translational and angular distributions, shedding valuable light on the nonadiabatic reaction dynamics. The calculated rate coefficients from 200 to 600 K are also in good agreement with the latest experimental measurements. More importantly, these calculations revealed that the reaction is controlled by intersystem crossing, rather than potential barriers.

Revisiting O(N) σ model at unphysical pion masses and high temperatures

Roy-equation analysis on lattice data of ππ scattering phase shifts at mπ=391 MeV reveals that the lowest f0 meson becomes a bound state under this condition. In addition, there is a pair of complex poles below threshold generated by crossing symmetry [X.-H. Cao , ]. We use the N/D method to partially recover crossing symmetry of the O(N) σ model amplitude at leading order of 1/N expansion, and qualitatively reproduce the pole structure and pole trajectories with varying pion masses as revealed by Roy-equation analyses. The σ pole trajectory with varying temperature is also discussed and found to be similar to its properties when varying mπ. As the temperature increases, the complex σ poles firstly move from the second Riemann sheet to the real axis becoming two virtual state poles, and then one virtual state pole moves to the first sheet turning into a bound state pole and finally tends to the pion pole position at high temperature which is as expected from the chiral symmetry restoration. Our results provide further evidence that the lowest f0 state extracted from experiments and lattice data plays the role of the σ meson in the spontaneous breaking of chiral symmetry. Finally, we also briefly discuss the problems of the effective potential in the situation when mπ and the temperature become large. Published by the American Physical Society 2024