Static Dipole Research Articles

Electronic structure with spin-orbit coupling effect of HfH molecule for laser cooling investigations

The electronic structure, including the spin–orbit coupling effect of the HfH molecule, has been studied to determine if it can be cooled through Doppler and Sysphus laser cooling techniques. The multi-reference configuration interaction plus Davidson correction (MRCI + Q) method has been used to calculate its potential energy curves (P.E.C.s) in the Ω(±) and 2s+1Ʌ(+/-) representation. The spectroscopic constants Te, Re, ωe, Be, αe, the dipole moment µe, and the dissociation energies De agree very well with previously published work. In addition, we present in this work twenty new doublet and quartet states in the Ω(±) representation. The electronic transition dipole moment curves (TDMCs) between the lowest-lying electronic states have been investigated for the Δ - Π, Π - ∑+ and Δ - Φ transitions among specific Ω(±) states. The Franck-Condon factors (FCFs), the Einstein coefficient of spontaneous emission Aν′ν, and the radiative lifetime τ have been computed for the investigated transitions. In addition, properties of the molecules' electronic and vibrational states, such as the static dipole moment curves (D.M.C.s), the ionic character fionic, and the rovibrational constants are calculated. We deduce from our results that the HfH molecule is indeed a laser-cooling candidate that can reach a temperature as low as the nK regime. We present a complementary scheme with suitable experimental parameters. These results can be of great interest to experimental spectroscopists interested in ultracold diatomic molecules and their applications.

Exploring the Potential of Residual Impurities in Germanium Detectors for MeV-Scale Dark Matter Detection

The direct detection of MeV-scale dark matter (DM) particles hinges on achieving an exceptionally low-energy detection threshold. Germanium (Ge) detectors, meticulously tailored with precise impurity compositions, hold the potential to enhance sensitivity to energy levels below the sub-electronvolt (sub-eV) range. This study explores the behavior of residual impurities inherent to Ge detectors at helium temperatures, unveiling a captivating freeze-out phenomenon leading to the formation of excited localized states known as dipole states. Using compelling evidence from relative capacitance measurements obtained from two detectors, we elucidate the transition of impurity atoms from free charge states to these dipole states as the temperature drops from 11 to 6.5 K. Our investigation comprehensively covers the intricate formation of these dipole states in both n-type and p-type impurities. Furthermore, we shed light on the electric field generated by these dipole states, revealing their ability to trap charges and facilitate the creation of cluster dipole states. Confirming findings from previous measurements, we establish that these excited dipole states exhibit a binding energy of less than 10 meV, offering an exceptionally low detection threshold for MeV-scale DM. Building upon this concept, we propose the development of a 1-kg Ge detector with internal charge amplification—an innovative approach poised to surpass electrical noise and enable the detection of MeV-scale DM with unprecedented sensitivity.

Solitons supported by a self-defocusing trap in a fractional-diffraction waveguide

We introduce a model which gives rise to self-trapping of fundamental and higher-order localized states in a one-dimensional nonlinear Schrödinger equation with fractional diffraction and the strength of the self-defocusing nonlinearity growing steeply enough from the center to periphery. The model can be implemented in a planar optical waveguide. Stability regions are identified for the fundamental and dipole (single-node) states in the plane of the Lévy index and the total power (norm), while states of higher orders are unstable. Evolution of unstable states is investigated too, leading to spontaneous conversion towards stable modes with fewer node.

Excitation Wavelength and Concentration Dependent Photophysical behaviour of Dipolar Molecular rotors in Solution: Role of Structural Modification

The present work demonstrates that the twisted intramolecular charge transfer (TICT) and Intramolecular charge transfer (ICT) process can be achieved by structural modification of a molecule. The DMMC (2-(4-(dimethylamino)benzylidene)malononitrile) and DMDC (2-(4-(dimethylamino)benzylidene)malononitrile) exhibit TICT and ICT state respectively via structural modification at the ground state. Solvent-dependent fluorescence enhancement of these molecules is monitored by comparing the relative intensity of locally excited (LE) and ICT emission band from excitation wavelength and concentration-dependent study.Both molecules display the ICT emission process at excited state depending upon excitation wavelength and concentration in solution. Interestingly, aggregation behaviour is also observed during excitation wavelength and concentration-dependent study in H2O. Solvent and excitation wavelength-dependent quenching and enhancement of fluorescence properties are also observed. Dipolar state and molecular orientation may play an important role in excitation and concentration-dependent fluorescence process in solution.

Enhanced intramolecular charge transfer and near-infrared fluorescence in 4-dimethylamino-chalcone analogues through extended conjugation: synthesis, photophysical properties, and theoretical modelling.

The distinctive characteristics of near-infrared fluorescent organic molecules render them indispensable across diverse applications, from energy harvesting to bioimaging and sensing technologies. In this work, we continue our investigation on the chalcone derivative, 4-dimethylamino-2'-hydroxychalcone (nDHC, n = 1; where n is the number of olefinic bonds), by expanding the number of central double bonds (n = 2 (2DHC) and n = 3 (3DHC)). Additionally, we also synthesized the structurally related chalcones lacking the OH group (DC, 2DC, 3DC) in order to obtain a comprehensive understanding of their effects on the intramolecular charge transfer (ICT). The results show remarkable bathochromic shifts in absorption and fluorescence peaks in solution as n increases. These shifts, 20 nm and 35 nm for absorption and 100 nm and 200 nm for fluorescence in 2DHC and 3DHC, respectively, signify enhanced ICT and a significant increase in the excited state's dipole moment. The presence of OH groups notably amplifies these shifts due to additional electron donation, influencing solute-solvent interactions in solution. Femtosecond fluorescence upconversion and transient absoprtion techniques unraveled distinct dynamics in these derivatives, exhibiting the dominance of vibrational cooling, solvation, and intramolecular motions, particularly in the larger conjugated systems 3DHC and 3DC. The observed changes in the femtosecond transinet absorption spectra suggest the existence of new active states in extended conjugation systems, indicating diverse intramolecular conformational states contributing to their relaxation dynamics. The results of this study provide invaluable insights into excited-state spectroscopy, offering a roadmap for tailoring chalcone derivatives for specific applications.

Polarizabilities of the negative ions of hydrogen and positronium in nonideal classical plasmas

We investigate the polarizability of the negative ions of hydrogen and positronium embedded in nonideal classical plasmas using correlated exponential wavefunctions. The interactions among the charged particles in plasmas have been taken care of by a pseudopotential, derived from a solution of Bogolyubov's hierarchy equations. The effects of nonideality of plasma on the ground state energies and the static and dynamic dipole polarizabilities of the negative ions have been studied in detail for wide range of nonideality. The results show interesting features.

Конформационная структура полиамфолитов на поверхности сферической металлической наночастицы при одновременном воздействии статического и переменного электрических полей

The simultaneous effect of external static and alternating electric fields on the composite nanosystem "gold spherical nanoparticle-polyampholyte" was studied. Radial and angular dependences of the polymer density were constructed, including in a narrow surface layer of the nanoparticle. In the case where the amplitude of the alternating dipole moment of the nanoparticle significantly exceeded the value of the static dipole moment, a ring-shaped fringe was formed in the equatorial region of the spherical gold nanoparticle. With an increase in the amplitude of the alternating electric field, the shape of the polyampholyte fringe changed from elongated in the direction of static polarization to swollen in the equatorial region of the nanoparticle. Oppositely charged links were located on those halves of the spherical nanoparticle relative to the equator, where opposite charges were induced due to the effect of the static electric field.

Electronic Structure Studies with Spin-Orbit Coupling Effect of the Molecule TlI

To study the low–lying electronic states of the TlI molecule, the electronic structure of this molecule has been investigated via an ab initio Complete Active Space Self Consistent Field and the Multireference Configuration Interaction with Davidson correction calculation (CASSCF/MRCI+Q). In the representations of 2s+1Λ(+/−) and (±), the adiabatic potential energy curves (PECs) along with static and transition dipole moment (DM) curves for 19 low-lying electronic states for TlI molecule have been investigated. For the low-lying electronic states of this molecule, the spectroscopic constants Re, Te, ωe, and Be, are provided. Based on the data obtained, this molecule is not a candidate for a Doppler laser cooling study.

Unraveling Synergistic Effect of Defects and Piezoelectric Field in Breakthrough Piezo-Photocatalytic N2 Reduction.

Piezo-photocatalysis is a frontier technology for converting mechanical and solar energies into crucial chemical substances and has emerged as a promising and sustainable strategy for N2 fixation. Here, for the first time, defects and piezoelectric field are synergized to achieve unprecedented piezo-photocatalytic nitrogen reduction reaction (NRR) activity and their collaborative catalytic mechanism is unraveled over BaTiO3 with tunable oxygen vacancies (OVs). The introduced OVs change the local dipole state to strengthen the piezoelectric polarization of BaTiO3 , resulting in a more efficient separation of photogenerated carrier. Ti3+ sites adjacent to OVs promote N2 chemisorption and activation through d-π back-donation with the help of the unpaired d-orbital electron. Furthermore, a piezoelectric polarization field could modulate the electronic structure of Ti3+ to facilitate the activation and dissociation of N2 , thereby substantially reducing the reaction barrier of the rate-limiting step. Benefitting from the synergistic reinforcement mechanism and optimized surface dynamics processes, an exceptional piezo-photocatalytic NH3 evolution rate of 106.7µmolg-1 h-1 is delivered by BaTiO3 with moderate OVs, far surpassing that of previously reported piezocatalysts/piezo-photocatalysts. New perspectives are provided here for the rational design of an efficient piezo-photocatalytic system for the NRR.

Nuclear Structure and Decay Data for A = 222 Isobars

Evaluated data are presented for 11 known A=222 nuclides (Bi, Po, At, Rn, Fr, Ra, Ac, Th, Pa, U, and Np), and relevant Jπ and T1/2 data for A=226 nuclei decaying by α-decay to A=222 nuclei. For 222Bi, only the isotopic identification is established with no measurement of its half-life. For 222Po, 222At, 222Fr, 222U, and 222Np, data are available only for the ground states, with static magnetic dipole and electric quadrupole moments, and charge radius measurements for the 222Fr ground state. For 222Ac and 222Pa, two low-lying levels are known from 226Pa α decay, and 226Np decay, respectively, but with no information about Jπ assignments and γ decays of these levels. For 222Pa, a long-lived isomeric state is known, decaying dominantly by α decay. 222Rn, 222Ra, and 222Th have been investigated in detail, the low-spin states by α decay and the high-spin studies of ground-state and octupole bands by in-beam γ-ray studies for all the three nuclei, as well as by Coulomb excitation for 222Rn and 222Ra. Low-spin levels in 222Ra have been investigated also through the β− decay of 222Fr. Half-lives of the excited states are known for 7 levels in 222Rn, 12 levels in 222Ra, and 3 levels in 222Th. Octupole deformations, with the presence of alternating-parity bands up to (16+) and (21−) in 222Rn, (20+) and (19−) in 222Ra, and (26+) and (25−) in 222Th, and with interband E1 transitions, have been established in these three nuclei. The present evaluation supersedes the previous A=222 ENSDF evaluations: (2011Si24), (1996El01), (1987El06) and (1977To14).

Observation of Superfluorescence of ZnO Nanosheets

ZnO nanostructures are attractive candidates as source media for realizing optoelectronic devices. Based on the comparison of cathodoluminescence images and scanning electron microscope morphology images, the mixing color images of ZnO nanosheets indicate that the emission of the ZnO nanosheet is emitted from its flat surface. In time‐resolved photoluminescence, a sharp emission pulse is observed after the delay time τD of 56 ps relative to zero time at the threshold excitation power, the pulse peak intensity exhibits a superlinear increase proportional to P2.7 (P is the excitation power density), the reduction of τD is proportional to , oscillation is demonstrated in the decay trace at high excitation power, and the time interval of two oscillation emissions is 36 ps. Experimental results indicate that superfluorescence (SF) is demonstrated at room temperature and it is assigned to coherent dipole states in the population version localized to approximately 3 nm thick ZnO nanosheet. SF of coherent dipole states is characterized by the delay time τD—the unique feature of SF and the Burnham–Chiao ringing behavior. Experimental observation of SF of ZnO nanosheets may have potential value for the investigation of room temperature many‐body quantum phenomena, coherent control, and applications for high‐performance optoelectronic devices.

Universal Pairwise Interatomic van der Waals Potentials Based on Quantum Drude Oscillators.

Repulsive short-range and attractive long-range van der Waals (vdW) forces play an appreciable role in the behavior of extended molecular systems. When using empirical force fields, the most popular computational methods applied to such systems, vdW forces are typically described by Lennard-Jones-like potentials, which unfortunately have a limited predictive power. Here, we present a universal parameterization of a quantum-mechanical vdW potential, which requires only two free-atom properties─the static dipole polarizability α1 and the dipole-dipole C6 dispersion coefficient. This is achieved by deriving the functional form of the potential from the quantum Drude oscillator (QDO) model, employing scaling laws for the equilibrium distance and the binding energy, and applying the microscopic law of corresponding states. The vdW-QDO potential is shown to be accurate for vdW binding energy curves, as demonstrated by comparing to the ab initio binding curves of 21 noble-gas dimers. The functional form of the vdW-QDO potential has the correct asymptotic behavior at both zero and infinite distances. In addition, it is shown that the damped vdW-QDO potential can accurately describe vdW interactions in dimers consisting of group II elements. Finally, we demonstrate the applicability of the atom-in-molecule vdW-QDO model for predicting accurate dispersion energies for molecular systems. The present work makes an important step toward constructing universal vdW potentials, which could benefit (bio)molecular computational studies.

Observation of quadrupolar and dipolar excitons in a semiconductor heterotrilayer.

Van der Waals (vdW) materials have opened up many avenues for discovery through layer assembly, as epitomized by interlayer dipolar excitons that exhibit electrically tunable luminescence, lasing and exciton condensation. Extending interlayer excitons to more vdW layers, however, raises fundamental questions concerning coherence within excitons and coupling between moiré superlattices at multiple interfaces. Here, by assembling angle-aligned WSe2/WS2/WSe2 heterotrilayers, we demonstrate the emergence of quadrupolar excitons. We confirm the exciton's quadrupolar nature by the decrease in its energy of 12 meV from coherent hole tunnelling between the two outer layers, its tunable static dipole moment under an external electric field and the reduced exciton-exciton interactions. At high exciton density, we also see signatures of a phase of oppositely aligned dipolar excitons, consistent with a staggered dipolar phase predicted to be driven by attractive dipolar interactions. Our demonstration paves the way for discovering emergent exciton orderings for three vdW layers and beyond.

Ab initio interaction potentials of alkali metal (M = Na and K)–rare gas (Rg = He, Ne, Ar, Kr, Xe and Rn) complexes

Spectroscopic properties and potential energy curves of alkali metal (M = Na and K) – rare gas (Rg = He, Ne, Ar, Kr, Xe and Rn) van der Waals molecules in their ground states have been studied in detail using spin-restricted open-shell coupled cluster with single and double excitations and perturbative contribution of connected triple excitations (RCCSD(T)) methods. The core-valence correlation (CV) effect was found to be crucial for M-RG molecules containing heavy rare gas atoms. The electronic energies were corrected for the basis set superposition error (BSSE) using the counterpoise method. Energies were extrapolated to the complete basis set (CBS) limit using a two-point scheme. The permanent electric dipole moments, static electric dipole polarizabilities and long-range dispersion coefficients were also calculated. The computed spectroscopic constants, vibrational levels and rotational constants were reported for M-RG and good agreement with the available experimental and theoretical values were found.

Synergism in the solvation of solvatochromic probes in binary mixtures with ionic liquids

The preferential solvation of two perichromic dyes, 4-amino-N-methylphthalimide (4-AMP) and Nile Red (NR) in binary mixtures of an ionic liquid ([bmim][X], where X = BF4, PF6, Tf2N and DCA) with a protic or non-protic solvent, was investigated, in search of examples of a synergetic or “hyperpolar” behavior. Synergism was generally observed in those mixtures where the two pure components had similar polarity values, according to the employed probe. A parallel was drawn between the observed synergism in these IL mixtures and the phenomenon of hydrotropism, also observed with organic solutes in aqueous IL mixtures. More generally, in binary mixtures with organic solvents, ionic liquids can act as solvatotropes, promoting the dye solvation by formation of solute-specific aggregates with all species present in the mixture. By stabilizing the dipolar excited state of 4-AMP or NR through hydrogen-bonds and electrostatic interactions in these aggregates, a “hyperpolar” milieu is generated, which surpasses the polarities of the two pure components. Solvatotropism seems to offer a more realistic picture than the solvent-exchange model, originally developed for simpler systems, to the phenomenon of preferential solvation in binary mixtures with ionic liquids.

Dielectric behaviour and dipole moment of binary mixtures containing certain amides in benzene

Certain polar amides(v) are dissolved in benzene, a nonpolar solvent(u) to prepare binary mixtures with different composition of the amides like acetanilide, N-N-dimethyl acetamide, N-methyl acetamide, acetamide and formamide. Static relative permittivity ɛ0uv , high frequency permittivity ɛ ∞uv for different weight fraction of polar solute at 30°C are determined. The dielectric behaviour of binary mixtures are investigated under electric field of low frequency by using the Debye model for polar liquids. Static dipole moment µs , dipole moment µv from conductivity measurements and µ t from bond angle and bond moment measurements are computed. The dipole moments are consequence of attractive interaction between the adjacent molecules in binary mixture due to variation of electron densities. Hydrogen bonding, associated charge distribution among the constituent molecules, changes in bond angle values are some of the factors that give rise to dipole moment of binary mixtures. Nearly equal and close values of µs , µv and µt proves the correctness of dielectric behaviour studies of amides- benzene binary mixtures.

Synergistic Mechanism of 0D Internal and Surface Defects Regulation Coupled with Pyroelectric Effects for Optimizing the Photoelectrocatalytic Properties of CdS

AbstractRational defect regulation is an effective way to enhance the performance of photoelectrocatalytic (PEC) water splitting. In this paper, we firstly constructed internal and surface defects to modulate the crystal structure of CdS, and investigated the synergistic impact of 0D (0‐dimensional) internal and surface defects regulation coupled with pyroelectric effects for optimizing the photoelectrocatalytic properties of CdS. It was found that the synergistic impact had a significant enhancement effect on the carrier separation and transfer, and the current density reached 3.93 mA/cm2 at 1.23 V vs. RHE increased by 16.38 times, meanwhile, the stability of the photoelectrodes was greatly promoted. The advantages and intrinsic relationships are also described: the formation of 0D dual‐type of defects alters the atomic arrangement in the crystal, optimizes the energy band structure, reduces carrier recombination, and increases carrier density. What's more, the introduction of defects induces electron redistribution and changes the state of dipoles inside the crystal, thus increasing built‐in electric field and generating more thermally generated carriers to optimize the pyroelectric effect. This work demonstrates the feasibility of defect modulation for optimizing pyroelectric performance and photocatalytic performance and bringing new light to PEC water splitting.

Tuning Surface Reactivity and Electric Field Strength via Intermetallic Alloying.

Many electrosynthesis reactions, such as CO2 reduction to multicarbon products, involve the formation of dipolar and polarizable transition states during the rate-determining step. Systematic and independent control over surface reactivity and electric field strength would accelerate the discovery of highly active electrocatalysts for these reactions by providing a means of reducing the transition state energy through field stabilization. Herein, we demonstrate that intermetallic alloying enables independent and systematic control over d-band energetics and work function through the variation of alloy composition and oxophilic constituent identity, respectively. We identify several intermetallic phases exhibiting properties that should collectively yield higher intrinsic activity for CO reduction compared to conventional Cu-based electrocatalysts. However, we also highlight the propensity of these alloys to segregate in air as a significant roadblock to investigating their electrocatalytic activity.

Tunable Rydberg–Rydberg transitions in helium with reduced sensitivity to dc electric fields by two-colour microwave dressing

The difference in the static electric dipole polarizabilities of the and Rydberg levels in helium has been eliminated by dressing the atom with a microwave field near resonant with the single-photon transition. For an amplitude dressing field, detuned by from the zero-field transition frequency, the dc Stark shift of the two-photon transition between these states remained within for electric fields up to . This transition was probed by single-color two-photon microwave spectroscopy, and by two-color two-photon spectroscopy with one strong additional dressing field and a weak probe field. For all measurements, the transition frequencies and Stark shifts were compared, and found to be in excellent quantitative agreement with the results of Floquet calculations of the energy-level structure of the Rydberg states in the presence of the dressing fields and applied dc electric fields. The two-color microwave dressing scheme demonstrated, with one field applied to null the differential polarizability of the Rydberg–Rydberg transition, and the second exploited to allow the two-photon transition to be employed to achieve tunable absorption of single-photons from a weak probe field, will facilitate improved coherence times and tunable single-photon absorption in hybrid cavity QED experiments with Rydberg atoms and superconducting microwave circuits.

Dual nature of low-energy isoscalar monopole and dipole states in light nuclei

Isoscalar monopole (IS0) and dipole (IS1) states located below and around the alpha-particle threshold Sα in prolate 24Mg are investigated within fully self-consistent Skyrme Quasiparticle Random-Phase Approximation (QRPA) approach. It is shown that these states demonstrate strong mean-field (MF) effects: dipole vorticity, deformation-induced monopole-quadrupole (IS0/IS2) and dipole-octupole (IS1/IS3) coupling. At the same time, the density distributions show precursors of a cluster structure. So we get a cluster/MF duality with a strong dominance of MF impact. IS0 QRPA results are compared with iThemba Lab and RCNP (α, α′) data.