Nuclear Configuration Research Articles

New Ab Initio Potential Energy Surfaces for NH3 Constructed from Explicitly Correlated Coupled-Cluster Methods.

Accurate calculation of ab initio potential energy surfaces (PESs) for the NH3 molecule is a difficult task because of the poor convergence of the standard CCSD(T) method with respect to the basis size. Currently, the best available NH3 PESs contain empirically refined parameters. In this paper, we show that CCSD(T)/aug-cc-pCV6Z calculations are not sufficient to properly describe the PES over a large range of nuclear configurations. However, the PES obtained by the extrapolation of the CCSD(T)/aug-cc-pCVXZ (X = T, Q, 5, and 6) energies to the complete basis set limit is closer to that based on the explicitly correlated CCSD(T)-F12a method using the cc-pCVQZ-F12 orbital basis set. All of the ab initio PESs constructed in this work include the following corrections: one electron relativistic effects, diagonal Born-Oppenheimer correction, and high-order electronic correlations (CCSDT, CCSDTQ, and CCSDTQP). Finally, the root-mean-square deviation between the predicted band centers obtained from our final "pure" ab initio PES and the experimental ones in the spectral region [0-7000] cm-1 is divided by two compared to the most accurate ab initio PES available in the literature.

Pseudo Jahn−Teller Origin of the Proton Tunneling in Zundel Cation Containing Water Clusters

The pseudo Jahn–Teller (PJT) origin of the proton transfer barrier in the Zundel cation at different O–O distances and in an H5O2+(H2O)4 cluster is revealed by means of ab initio calculations of their electronic structures and the adiabatic potential energy curves. The vibronic constants in this approach were estimated by fitting the ab initio calculated adiabatic potential to its analytical expression. It is shown also that the high-symmetry nuclear configurations ofproton-centered water clusters of the type H+(H2O)n (n = 6, 4, 3) are unstable with respect to the low-symmetry nuclear distortions leading to forming the dihydronium cation H5O2+ and the appropriate number of water molecules: H2n + 1On+ → (n – 2)H2O + H5O2+. The reason for this instability and the subsequent decay is the PJT coupling between the ground and excited electronic states.

First observation of high-K isomeric states in $$^{249}$$Md and $$^{251}$$Md

Decay spectroscopy of the odd-proton nuclei $^{249}$Md and $^{251}$Md has been performed. High-$K$ isomeric states were identified for the first time in these two nuclei through the measurement of their electromagnetic decay. An isomeric state with a half-life of $2.8(5)$ ms and an excitation energy $\geq 910$ keV was found in $^{249}$Md. In $^{251}$Md, an isomeric state with a half-life of $1.4(3)$ s and an excitation energy $\geq 844$ keV was found. Similarly to the neighbouring $^{255}$Lr, these two isomeric states are interpreted as 3 quasi-particle high-$K$ states and compared to new theoretical calculations. Excited nuclear configurations were calculated within two scenarios: via blocking nuclear states located in proximity to the Fermi surface or/and using the quasiparticle Bardeen-Cooper-Schrieffer method. Relevant states were selected on the basis of the microscopic-macroscopic model with a deformed Woods-Saxon potential. The most probable candidates for the configurations of $K$-isomeric states in Md nuclei are proposed.

Study of the Electronic Structure of Alkali Peroxides and Their Role in the Chemistry of Metal-Oxygen Batteries.

We use a multiconfigurational and correlated ab initio method to investigate the fundamental electronic properties of the peroxide MO2– (M = Li and Na) trimer to provide new insights into the rather complex chemistry of aprotic metal–O2 batteries. These electrochemical systems are largely based on the electronic properties of superoxide and peroxide of alkali metals. The two compounds differ by stoichiometry: the superoxide is characterized by a M+O2– formula, while the peroxide is characterized by [M+]2O22–. We show here that both the peroxide and superoxide states necessarily coexist in the MO2– trimer and that they correspond to their different electronic states. The energetic prevalence of either one or the other and the range of their coexistence over a subset of the MO2– nuclear configurations is calculated and described via a high-level multiconfigurational approach.

Single-particle and collective excitations in the transitional nucleus 166Os

The mean lifetimes of the lowest energy 2+, 8+ and 9− states in 166Os have been measured using the recoil distance Doppler-shift method in conjunction with a selective recoil-decay tagging technique. These measurements extend studies into the most neutron-deficient mass region accessible to current experimental methods. The B(E2; 2+ → 0+) = 7(2) W.u. extracted from these measurements is markedly lower than those observed in the heavier even-mass Os isotopes. The 8+ and 9− states yield reduced transition probabilities that are consistent with single-particle transitions. While these values may indicate a departure from collective structure, the level scheme and the underlying nuclear configurations can also be interpreted in terms of a simple collective picture. This contrasting behaviour suggests an intriguing dichotomy in the description of heavy transitional nuclei.

Theory and applications of nuclear direct reactions

These lectures, held at a school at the Galileo Galilei Institute for Theoretical Physics, give a survey of the formalism, the methods and achievements of nuclear direct reaction theory. After recapitulating the principles of quantum scattering theory, projection techniques are used to reduce the complexities of nuclear reactions to the manageable level of a set of a few selected coupled channels interacting via effective operators. Direct reactions are introduced as fast reactions proceeding preferentially through the excitation of doorway components of the nuclear many-body configurations, corresponding to a separation of scales in energy and momentum transfer. The concept of the optical model is introduced and applied to elastic scattering on nuclei. The coupled channel T-matrix formalism is discussed for pion-induced reactions on the nucleon. Applications of direct reaction to theory are illustrated for transfer reactions, inelastic scattering, and single and double charge exchange reactions with light and heavy ions.

Single-cell landscape of nuclear configuration and gene expression during stem cell differentiation and X inactivation

BackgroundMammalian development is associated with extensive changes in gene expression, chromatin accessibility, and nuclear structure. Here, we follow such changes associated with mouse embryonic stem cell differentiation and X inactivation by integrating, for the first time, allele-specific data from these three modalities obtained by high-throughput single-cell RNA-seq, ATAC-seq, and Hi-C.ResultsAllele-specific contact decay profiles obtained by single-cell Hi-C clearly show that the inactive X chromosome has a unique profile in differentiated cells that have undergone X inactivation. Loss of this inactive X-specific structure at mitosis is followed by its reappearance during the cell cycle, suggesting a “bookmark” mechanism. Differentiation of embryonic stem cells to follow the onset of X inactivation is associated with changes in contact decay profiles that occur in parallel on both the X chromosomes and autosomes. Single-cell RNA-seq and ATAC-seq show evidence of a delay in female versus male cells, due to the presence of two active X chromosomes at early stages of differentiation. The onset of the inactive X-specific structure in single cells occurs later than gene silencing, consistent with the idea that chromatin compaction is a late event of X inactivation. Single-cell Hi-C highlights evidence of discrete changes in nuclear structure characterized by the acquisition of very long-range contacts throughout the nucleus. Novel computational approaches allow for the effective alignment of single-cell gene expression, chromatin accessibility, and 3D chromosome structure.ConclusionsBased on trajectory analyses, three distinct nuclear structure states are detected reflecting discrete and profound simultaneous changes not only to the structure of the X chromosomes, but also to that of autosomes during differentiation. Our study reveals that long-range structural changes to chromosomes appear as discrete events, unlike progressive changes in gene expression and chromatin accessibility.

Optimal Representation of the Nuclear Ensemble: Application to Electronic Spectroscopy.

Nuclear densities are frequently represented by an ensemble of nuclear configurations or points in the phase space in various contexts of molecular simulations. The size of the ensemble directly affects the accuracy and computational cost of subsequent calculations of observable quantities. In the present work, we address the question of how many configurations do we need and how to select them most efficiently. We focus on the nuclear ensemble method in the context of electronic spectroscopy, where thousands of sampled configurations are usually needed for sufficiently converged spectra. The proposed representative sampling technique allows for a dramatic reduction of the sample size. By using an exploratory method, we model the density from a large sample in the space of transition properties. The representative subset of nuclear configurations is optimized by minimizing its Kullback-Leibler divergence to the full density with simulated annealing. High-level calculations are then performed only for the selected subset of configurations. We tested the algorithm on electronic absorption spectra of three molecules: (E)-azobenzene, the simplest Criegee intermediate, and hydrated nitrate anion. Typically, dozens of nuclear configurations provided sufficiently accurate spectra. A strongly forbidden transition of the nitrate anion presented the most challenging case due to rare geometries with disproportionately high transition intensities. This problematic case was easily diagnosed within the present approach. We also discuss various exploratory methods and a possible extension to dynamical simulations.

Two-Photon Excited Fluorescence Dynamics in Enzyme-Bound NADH: the Heterogeneity of Fluorescence Decay Times and Anisotropic Relaxation.

The dynamics of polarized fluorescence in NADH in alcohol dehydrogenase (ADH) in buffer solution has been studied using the TCSPC spectroscopy. A global fit procedure was used for determination of the fluorescence parameters from experiment. The interpretation of the results obtained was supported by ab initio calculations of the NADH structure. A theoretical model was developed describing the polarized fluorescence decay in ADH-NADH complexes that considered several interaction scenarios. A comparative analysis of the polarization-insensitive fluorescence decay using multiexponential fitting models has been carried out. As shown, the origin of a significant enhancement of the decay time in the ADH-NADH complex can be attributed to the decrease of nonradiative relaxation rates in the nicotinamide ring in the conditions of the apolar binding site environment. The existence of a single decay time in the ADH-NADH complex in comparison with two decay times observed in free NADH was attributed to a single NADH unfolded conformation in the ADH binding site. Comparison of the experimental data with the theoretical model suggested the existence of an anisotropic relaxation time of about 1 ns that is related with the rotation of fluorescence transition dipole moment due to the rearrangement of the excited state NADH nuclear configuration.

Study of the Static and Dynamic Nuclear Properties and Form Factors for Some Magnesium Isotopes 29-34 Mg

Nuclear structure of 29-34Mg isotopes toward neutron dripline have been investigated using shell model with Skyrme-Hartree–Fock calculations. In particular nuclear densities for proton, neutron, mass and charge densities with their corresponding rms radii, neutron skin thicknesses and inelastic electron scattering form factors are calculated for positive low-lying states. The deduced results are discussed for the transverse form factor and compared with the available experimental data. It has been confirmed that the combining shell model with Hartree-Fock mean field method with Skyrme interaction can accommodate very well the nuclear excitation properties and can reach a highly descriptive and predictive power when investigating different nuclear configurations of stable and unstable nuclei.

Exotic toroidal and superdeformed configurations in light atomic nuclei: Predictions using a mean-field Hamiltonian without parametric correlations

Mean-field calculations in multidimensional deformation spaces are performed and the shape coexistence and isomers generated by exotic nuclear configurations and toroidal and superdeformed ones are addressed. We use a phenomenological mean-field Hamiltonian of Woods-Saxon type with its universal parametrization involving eight parameters fixed once for all for the full periodic table. Original parametric correlations existing in this type of Hamiltonians are removed using methods of inverse problem theory of applied mathematics. Stochastic analysis of uncertainties of the final nuclear energy predictions with the obtained correlation-free parametrization is performed and the viability tests are illustrated and discussed. Prediction capacities of resulting model related to the description of the nuclear shape properties are cross-checked using the experimental information available, revealing full coherence. Presented results encourage experimental verification of predicted exotic structures; suggestions related to identification possibilities are formulated and discussed.

Recombination of Polaronic Electron-Hole Pairs in Hematite Determined by Nuclear Quantum Tunneling.

Here, we investigate the intrinsic nonradiative recombination mechanism in hematite single crystals that decides the photocarrier lifetime under solar illumination. On the basis of the small polaron theory, we propose that the photogenerated electron-hole pair along with its induced lattice deformation in hematite could be treated as a pseudocoordination-complex (PCC) dispersed in a solid medium. We demonstrate that the nonradiative recombination rate at different temperatures determined from the transient absorption spectroscopy can be excellently described by the nonradiative transition theory developed previously for parallels of the PCC model. Our finding suggests that at room temperature the nonradiative recombination in hematite substantially depends on the probability of quantum tunneling of the nuclear configuration.

New approach to intranuclear cascades with quantum Monte Carlo configurations

We propose a novel approach to intranuclear cascades which takes as input quantum MonteCarlo nuclear configurations and uses a semi-classical, impact-parameter based algorithm to modelthe propagation of protons and neutrons in the nuclear medium. We successfully compare oursimulations to available proton-carbon scattering data and nuclear-transparency measurements. Byanalyzing the dependence of the simulated observables upon the ingredients entering our intranuclearcascade algorithm, we provide a quantitative understanding of their impact. Particular emphasisis devoted to the role played by nuclear correlations, the Pauli exclusion principle, and interactionprobability distributions.

Hybrid quantum-classical algorithms for solving quantum chemistry in Hamiltonian–wave-function space

The variational quantum eigensolver (VQE) typically optimizes variational parameters in a quantum circuit to prepare eigenstates for a quantum system. Its application to many problems may involve a group of Hamiltonians, e.g., a Hamiltonian of a molecule is a function of the nuclear configurations. In this paper we incorporate derivatives of the Hamiltonian into the VQE and develop some hybrid quantum-classical algorithms, which explore both Hamiltonian and wave-function spaces for solving quantum chemistry problems more efficiently. For geometry optimization, we propose a mutual gradient-descent algorithm that updates the parameters of the Hamiltonian and wave function alternately, which can give a rapid convergence towards equilibrium structures of molecules as demonstrated in numerical simulations. Moreover, to speed up the calculation of the energy potential surface, we establish differential equations that govern how the optimized variational parameters of the wave function change with the intrinsic parameters of the Hamiltonian. Our study suggests a direction for a hybrid quantum-classical algorithm for solving quantum systems more efficiently by considering spaces of both the Hamiltonian and the wave function.

A Machine Learning Approach for MP2 Correlation Energies and Its Application to Organic Compounds.

A proper treatment of electron correlation effects is indispensable for accurate simulation of compounds. Various post-Hartree-Fock methods have been adopted to calculate correlation energies of chemical systems, but time complexity usually prevents their usage in a large scale. Here, we propose a density functional approximation, based on machine learning using neural networks, which can be readily employed to produce results comparable to second-order Møller-Plesset perturbation (MP2) ones for organic compounds with reduced computational cost. Various systems have been tested and the transferability across basis sets, structures, and nuclear configurations has been evaluated. Only a small number of molecules at the equilibrium structure has been needed for the training, and generally less than 5% relative error has been achieved for structures outside the training domain and systems containing about 140 atoms. In addition, this approach has been applied to make predictions on correlation energies of nuclear configurations extracted from density functional theory-based molecular dynamics trajectories with only one or two structures as training data.

Polarized electron-deuteron deep-inelastic scattering with spectator nucleon tagging

Background: DIS on the polarized deuteron with detection of a proton in the nuclear breakup region (spectator tagging) represents a unique method for extracting the neutron spin structure functions and studying nuclear modifications. The tagged proton momentum controls the nuclear configuration during the DIS process and enables a differential analysis of nuclear effects. Such measurements could be performed with the future electron-ion collider (EIC) and forward proton detectors if deuteron beam polarization could be achieved. Purpose: Develop theoretical framework for polarized deuteron DIS with spectator tagging. Formulate procedures for neutron spin structure extraction. Methods: A covariant spin density matrix formalism is used to describe general deuteron polarization in collider experiments (vector/tensor, pure/mixed). Light-front (LF) quantum mechanics is employed to factorize nuclear and nucleonic structure in the DIS process. A 4-dimensional representation of LF spin structure is used to construct the polarized deuteron LF wave function and efficiently evaluate the spin sums. Free neutron structure is extracted using the impulse approximation and analyticity in the tagged proton momentum (pole extrapolation). Results: General expressions of the polarized tagged DIS observables in collider experiments. Analytic and numerical study of the polarized deuteron LF spectral function and nucleon momentum distributions. Practical procedures for neutron spin structure extraction from the tagged deuteron spin asymmetries. Conclusions: Spectator tagging provides new tools for precise neutron spin structure measurements. D-wave depolarization and nuclear binding effects can be eliminated through the tagged proton momentum dependence. The methods can be extended to tensor-polarized observables, spin-orbit effects, and diffractive processes.

Circumflex Nuclear Configurations in Yucatecan Spanish as a Supraregional Feature: The Roles of Bilingualism and Gender.

In this paper, we study the nuclear configurations of declarative broad focus utterances in Yucatecan Spanish, a Mexican variety spoken in southeast Mexico in contact with Yucatec Maya, from a sociolinguistic perspective. We draw on a corpus of 276 utterances elicited from 16 speakers, eight Maya-Spanish bilinguals (four female/four male) and eight Spanish monolinguals (four female/four male). We particularly concentrate on the roles of bilingualism, gender, and their relationship to local (Hispanic) identity. Although the intonation of Yucatecan Spanish is known to be very different from Central Mexican Spanish, we find in our data a considerable number of contours that Martín Butragueño (2017) refers to as typical "Central Mexican circumflex intonation" (p. 153). What is more, this feature is distributed unevenly among speaker groups in our data. First of all, it is much more frequent in the bilingual than in the monolingual group. We suggest that this is due to the monolinguals' higher degree of identification with the local Spanish language and culture (whereas the bilingual speakers are more oriented toward the Mayan language and culture and less toward the local Spanish ones; see Uth, 2018b). Secondly, as regards gender, there are many sociolinguistic works that suggest that women tend to be less oriented toward local vernaculars than men. Building on that, we argue that a greater decrease of the supraregional circumflex configuration within the monolingual male group than within the monolingual female is to be expected. However, this hypothesis is not confirmed by our data.

Spectroscopy of proton-rich 79Zr: Mirror energy differences in the highly-deformed fpg shell

Energy differences between isobaric analogue states have been extracted for the A=79, 79Zr/79Y mirror pair following their population via nucleon-knockout reactions from intermediate-energy rare-isotope beams. These are the heaviest nuclei where such measurements have been made to date. The deduced mirror energy differences (MED) are compared with predictions from a new density-functional based approach, incorporating isospin-breaking effects of both Coulomb and nuclear charge-symmetry breaking and configuration mixing.

Individual empathy levels affect gradual intonation-meaning mapping: The case of biased questions in Salerno Italian

The paper investigates the interplay between intonational cues and individual variability in the perceptual assessment of speakers’ epistemic bias in Salerno Italian yes-no questions. We present a perception experiment in which we manipulated pitch span within the nuclear configuration (both nuclear accent and boundary tone) to predict degree of perceived positive bias (i.e., expected positive answer) to yes-no question stimuli. Our results show that a wider pitch span within the nuclear region predicts a higher degree of perceived positive bias, while negative bias is predicted by narrow pitch span. Crucially, though, two interacting sources of listener variability were uncovered, i.e., prolonged exposure to a non-native dialect as well as degree of empathy (i.e., Empathy Quotient, EQ). Exposure to non-native phonological systems was found to affect the way pitch span is mapped onto perceived epistemic bias, through category interference, though mediated by EQ levels. Specifically, high-empathy listeners were more affected by degree of non-native dialect exposure. EQ scores were hence found to have an effect on gradual span manipulation by interacting with the dialect exposure effect. These results advance our understanding of the intonation-meaning mapping by taking into account both the impact of gradual phonetic cues on meaning processing as well as uncovering sources of cognitive variability at the perceiver’s level.

One-step automated bioprinting-based method for cumulus-oocyte complex microencapsulation for 3D in vitro maturation

Three-dimensional in vitro maturation (3D IVM) is a promising approach to improve IVM efficiency as it could prevent cumulus-oocyte complex (COC) flattening and preserve its structural and functional integrity. Methods reported to date have low reproducibility and validation studies are limited. In this study, a bioprinting based production process for generating microbeads containing a COC (COC-microbeads) was optimized and its validity tested in a large animal model (sheep). Alginate microbeads were produced and characterized for size, shape and stability under culture conditions. COC encapsulation had high efficiency and reproducibility and cumulus integrity was preserved. COC-microbeads underwent IVM, with COCs cultured in standard 2D IVM as controls. After IVM, oocytes were analyzed for nuclear chromatin configuration, bioenergetic/oxidative status and transcriptional activity of genes biomarker of mitochondrial activity (TFAM, ATP6, ATP8) and oocyte developmental competence (KHDC3, NLRP5, OOEP and TLE6). The 3D system supported oocyte nuclear maturation more efficiently than the 2D control (P<0.05). Ooplasmic mitochondrial activity and reactive oxygen species (ROS) generation ability were increased (P<0.05). Up-regulation of TFAM, ATP6 and ATP8 and down-regulation of KHDC3, NLRP5 expression were observed in 3D IVM. In conclusion, the new bioprinting method for producing COC-microbeads has high reproducibility and efficiency. Moreover, 3D IVM improves oocyte nuclear maturation and relevant parameters of oocyte cytoplasmic maturation and could be used for clinical and toxicological applications.