Excitation Of States Research Articles

Uranyl–Nickel(II) Cation–Cation Interaction in a Triperiodic Framework with cis‐1,2‐Cyclohexanedicarboxylate and Isonicotinate Ligands

Uranyl and nickel(II) nitrates have been reacted with cis‐1,2‐cyclohexanedicarboxylic (H2chdc) and isonicotinic (Hint) acids under solvo‐hydrothermal conditions, giving the heterometallic, mixed‐ligand complex [(UO2)2Ni(chdc)2(int)2]⋅CH3CN (1). The uranyl cation is bound to carboxylate groups of both ligands while NiII is attached to two carboxylate and two nitrogen donors, with two strong additional interactions with uranyl oxo groups giving a nearly regular octahedral environment. The short Ni–O(oxo) bond length of 2.114(3) Å amounts to 67% of the sum of van der Waals radii. The trimetallic (UO2)2Ni6+ clusters thus formed are assembled by chdc2– ligands into linear chains which are further bridged by int– links to give a triperiodic framework with the dia topology, in which small channels encompass two rows of acetonitrile solvent molecules. Complex 1 does not display uranyl luminescence under excitation in the solid state.

High-sensitivity multi-gas detection using dual-ridge metasurface emitters with polarization-distinguishable emission spectra

The metasurface thermal emitter offers an energy-efficient, compact, and sensitive solution as a radiation source for non-contact gas detection, enabling the “molecular fingerprint” technique to be widely applied, from medical diagnostics to environmental monitoring. However, most narrowband emitters are designed for a single target gas, hindering the miniaturization of multi-gas detection systems. In this work, a one-dimensional dual-ridge grating emitter is employed, achieving dual-band and tri-band polarization-distinguishable emission spectra through the excitation of Fabry-Perot (FP) resonances and quasi-bound states in the continuum (qBICs). These emission spectra can be readily matched to multiple non-overlapping absorption peaks of gases such as CH4, CO2, CO, NO, and NH3 within the 3–6 µm range, thereby reducing the impact of mixed gases on measurements. Compared to conventional metal-dielectric-metal structures, the use of a single metal layer results in lower material losses, enabling higher Q-factors and more pronounced directional radiation intensity variations. Furthermore, adjusting the asymmetry to modulate the qBIC-excited absorption peaks does not affect the Q-factor of the FP resonance absorption, thus achieving high-sensitivity multi-band gas detection. This work provides a promising approach for the miniaturization and integration of multi-gas channel detection, facilitating more accurate and sensitive sensing strategies.

Effect of Photon Vortex Generated in Extremely Strong Magnetic Fields on Stellar Nucleosynthesis

It is thought that photon vortices are predominantly produced in extremely strong magnetic fields in the Universe. Because the photon vortex may cause significant large angular momentum transfer in interactions with atomic nuclei, stellar nucleosynthesis in such astrophysical environments is affected. In the present study, we calculate the ratios of the photon absorption transition probabilities of photon vortices with Bessel wave to photons described by the plane wave. The result shows enhancement of excitation of states with large total angular momentum by optimization of the divergence angle of the incident photon vortex in momentum space. However, the average cross section for the photon vortex turns out to be identical with that for the plane wave. Therefore, even when Bessel photons are predominantly produced in astrophysical environments, the isotopic abundances of the synthesized elements are not changed.

Stochastic Resolution of Identity to CC2 for Large Systems: Ground State and Triplet Excitation Energy Calculations.

An implementation of stochastic resolution of identity to the CC2 (sRI-CC2) ground state energy followed by triplet excitation energy calculations is presented. A set of stochastic orbitals is introduced to further decouple the expensive 4-index electron repulsion integrals on the basis of RI approximation. A Laplace transformation of the orbital energy difference denominators into numerical summations is adopted to obtain a third-order overall scaling. We select a series of hydrogen dimer chains with nearly thousands of electrons, as well as some other molecules, for sRI-CC2 energies and test the accuracy and time consumption in comparison with those of RI-CC2. Our sRI-CC2 results reproduce a modest agreement with the RI-CC2 in Q-Chem program package and it allows a steep scaling reduction from O(N5) to O(N3). Besides, the unrestricted sRI-CC2 calculations also fit well with the restricted results. Thus, our sRI-CC2 implementation of ground state energy and triplet excitation energy provides a cost-efficient alternative approach, especially for some large-sized systems.

Simultaneous Probing of Electron Density and Temperature Dynamics Inside Air Plasma with Intense Terahertz Pulses

AbstractAir plasma induced by ultrafast laser pulses is an extraordinary source of electromagnetic waves, emitting microwave, terahertz (THz) radiation, and cavityless lasing in the near‐infrared and visible ranges. The temporal dynamics of the electron density have been revealed by optical pump‐probe techniques, while the evolution of the electron temperature remains elusive due to a lack of suitable methods. Here, it is demonstrated that the intense THz‐field‐enhanced fluorescence emission from the excited molecules of nitrogen is a novel tool that allows to explore the complex dynamics of the plasma density and electron temperature simultaneously. Two relaxation times of electrons in air plasma are observed and interpreted as a competition between the excitation of a triplet state by laser or THz‐field‐heated electrons and the dissociative recombination of nitrogen molecular ions. Based on the theoretical simulations, the tens of picoseconds relaxation process is attributed to the ultrafast temperature decrease, while the longer relaxation in the range of hundreds of picoseconds is ascribed to the decay of electron density. The temporal relaxation of both the electron density and temperature revealed by applying an intense THz field provides further insights into the laser‐air plasma interaction and will benefit the engineering of this exceptional source.

Theoretical analysis of a refractive index sensor based on optical Tamm state of graphene metastructure under arbitrary polarization deflection angle

In this paper, a refractive index sensor based on a metastructure (MS) is proposed, which achieves sensing through the sharp valleys formed in the reflection spectrum by the excitation of optical Tamm states (OTS) by gyroidal graphene. Differences in the refractive index of the filling medium in the pores of gyroidal graphene will cause shifts in the reflection valleys. The graphene layer is followed by a periodic structure consisting of alternating zirconium dioxide (ZrO2) and α-molybdenum trioxide (α-MoO3). The 4 × 4 transfer matrix method (TMM) is used for the calculation of the results, which allows the case of arbitrary polarization deflection angles ϕ to be considered in the discussion. Different values of ϕ can lead to a switch in the dominance of the sensor, specifically, the structure has a larger linear interval but lower sensitivity at ϕ = 0°, which is the opposite of the situation at ϕ = 90°. The sensor can be used in a variety of scenarios such as biochemical sensing, gas detection, etc, and brings the polarization deflection angle of the incident wave into the discussion.

Optical force and torque in near-field excitation of C3H6: A first-principles study using RT-TDDFT.

Optical trapping is an effective tool for manipulating micrometer-sized particles, although its application to nanometer-sized particles remains difficult. The field of optical trapping has advanced significantly, incorporating more advanced techniques such as plasmonic structures. However, single-molecule trapping remains a challenge. To achieve a deeper understanding of optical forces acting on molecular systems, a first-principles approach to analyze the optical force on molecules interacting with a plasmonic field is crucial. In our study, the optical force and torque induced by the near-field excitation of C3H6 were investigated using real-time time-dependent density functional theory calculations on real-space grids. The near field from the scanning tunneling probe was adopted as the excitation source for the molecule. The optical force was calculated using the polarization charges induced in the molecule based on Lorentz force. While the optical force and torque calculated as functions of the light energy were in moderate agreement with the oscillator strengths obtained from the far-field excitation of C3H6, a closer correspondence was achieved with the power spectrum of the induced dipole moment using near-field excitation. Time-domain analysis of the optical force suggests that the simultaneous excitation of multiple excited states generally weakens the force because of mismatches between the directions of the induced polarization and the electric field. This study revealed a subtle damping mechanism for the optical force arising from intrinsic electronic states and the influence of beating.

Bound-state confinement after trap-expansion dynamics in integrable systems

Abstract Integrable systems possess stable families of quasiparticles, which are composite objects (bound states) of elementary excitations. Motivated by recent quantum computer experiments, we investigate bound-state transport in the spin- 1 / 2 anisotropic Heisenberg chain (XXZ chain). Specifically, we consider the sudden vacuum expansion of a finite region A prepared in a non-equilibrium state. In the hydrodynamic regime, if interactions are strong enough, bound states remain confined in the initial region. Bound-state confinement persists until the density of unbound excitations remains finite in the bulk of A. Since region A is finite, at asymptotically long times bound states are ‘liberated’ after the ‘evaporation’ of the unbound excitations. Fingerprints of confinement are visible in the space-time profiles of local spin-projection operators. To be specific, here we focus on the expansion of the p-Néel states, which are obtained by repetition of a unit cell with p up spins followed by p down spins. Upon increasing p, the bound-state content is enhanced. In the limit p → ∞ one obtains the domain-wall initial state. We show that for p < 4, only bound states with n > p are confined at large chain anisotropy. For p ≳ 4 , bound states with n = p are also confined, consistent with the absence of transport in the limit p → ∞ . The scenario of bound-state confinement leads to a hierarchy of timescales at which bound states of different sizes are liberated, which is also reflected in the dynamics of the von Neumann entropy.

Inverse opal optical Tamm state for sensing applications

We report the excitation of optical Tamm states (OTS) in inverse opal (IO) - based three-dimensional photonic crystal on a flat metal substrate, validated through both numerical simulations and experimental observations. Large area, uniform Tamm inverse opal (Tamm-IO) structures were fabricated without the use of any corrosive chemicals. Upon infiltration of non-reactive solvents such as methanol and ethanol into the IO, a noticeable shift of the OTS, consistent with our simulations is observed, and the temporal dynamics of the same have been investigated. The experimentally obtained sensitivity is ∼ 110 nm/RIU which is of the same order as the computed value, making the IO OTS to be an attractive sensing tool.

Worldsheet kinematics, dressing factors and odd crossing in mixed-flux AdS3 backgrounds

String theory on AdS3 × S3 × T4 geometries supported by a combination of NS-NS and R-R charges is believed to be integrable. We elucidate the kinematics and analytic structure of worldsheet excitations in mixed charge and pure NS-NS backgrounds, when expressed in momentum, Zhukovsky variables and the rapidity u which appears in the quantum spectral curve. We discuss the relations between fundamental and bound state excitations and the role of fusion in constraining and determining the S matrices of these theories. We propose a scalar dressing factor consistent with a novel u-plane periodicity and comment on its close relation to the XXZ model at roots of unity. We solve the odd part of crossing and show that our solution is consistent with fusion and reduces in the relativistic limit to dressing phases previously found in the literature.

Constraining the axial-vector X17 interpretation with 12C data

Recent findings of an unexpected, narrow resonance in the e+e− decay spectra of excited states of 8Be, 4He and 12C by the ATOMKI collaboration have received considerable experimental and theoretical attention, whereby a new, 17-MeV vector-like or axial-vector-like boson termed X17 was conjectured as an explanation of the anomaly. Further analysis of all existing constraints disfavors a vector X17 scenario. For a similar analysis of the axial-vector scenario, a calculation of the reduced matrix element of a spin-dipole operator between the excited nuclear state 12C(17.23) and the carbon ground state is required. In the present work, we compute the aforementioned reduced matrix element under the assumption that the state 12C(17.23) is well represented by the 2s1/21p3/2−1 particle-hole shell-model excitation of the ground state, as supported by experimental data. Within such a framework, our results indicate that, like the vector scenario, the axial-vector interpretation of X17 shows strong tensions with the other existing constraints on the nucleon coupling of a conjectured X17.

Highly Tunable Light Absorber Based on Topological Interface Mode Excitation of Optical Tamm State.

Optical absorbers based on Tamm plasmon states are known for their simple structure and high operational efficiency. However, these absorbers often have limited absorption channels, and it is challenging to continuously adjust their light absorption rates. Here, we propose a Tamm plasmon state optical absorber composed of a layered stack structure consisting of one-dimensional topological photonic crystals and graphene nano-composite materials. Using the four-by-four transfer matrix method, we investigate the structural relationship of the absorber. Our results reveal that topological interface states (TISs) effectively excite the optical Tamm state (OTS), leading to multiple absorption peaks. This expands the number of absorption channels, with the coupling number of the TIS determining the transmission quality of these channels-a value further adjustable by the period number of the photonic crystals. Tuning the filling factor, refractive index, and thickness of the graphene nano-composite material allows for a wide range of control over the device's absorption rate, from 0 to 1. Additionally, adjusting the defect layer thickness, incident angle, and Fermi energy enables us to control the absorber's operational bandwidth and the switching of its absorption effect. This work presents a new approach to expanding the tunability of optoelectronic devices.

Energy level spectrum and lattice polarization of polaron in metal halide perovskite parabolic quantum wells

In this study, polaron effect in 2D metal halide perovskite materials (TMHPMs), which naturally form quantum well (QW) structures, has been investigated. Polarization of carriers and lattice within these structures was explored based on unitary transformation and variational methods. Specifically, lattice polarization and energy level transition spectra of strong coupling polaron in parabolic potential metal halide perovskite QWs (MAPbCl3, MAPbBr3, and MAPbI3) were studied. Also, we calculated ground and first excited state energies, excitation energy, transition frequency, and vibration frequency of a TMHPM QWs. Our results indicated that parabolic potential confinement intensity affected related physical quantities, which provided insight to investigate metal halide perovskite materials and polaron effect.

Controllable Goos-Hänchen Shift in Photonic Crystal Heterostructure Containing Anisotropic Graphene

In this study, we investigate the electrically and magnetically tunable Goos–Hänchen (GH) shift of a reflected light beam at terahertz frequencies. Our study focuses on a photonic crystal heterostructure incorporating a monolayer anisotropic graphene. We observe a tunable and enhanced GH shift facilitated by a drastic change in the reflected phase at the resonance angle owing to the excitation of the topological edge state. Considering the quantum response of graphene, we demonstrate the ability to switch positive and negative GH shifts through the manipulation of graphene’s conductivity properties. Moreover, we show that the GH shift can be actively tuned by the external electric field and magnetic field, as well as by controlling the structural parameters of the system. We believe that this tunable and enhanced GH shift scheme offers excellent potential for preparing terahertz shift devices.

Maximizing Nanoscale Downshifting Energy Transfer in a Metallosupramolecular Cr(III)-Er(III) Assembly.

Pseudo-octahedral CrIIIN6 chromophores hold a unique appeal for low-energy sensitization of NIR lanthanide luminescence due to their exceptionally long-lived spin-flip excited states. This allure persists despite the obstacles and complexities involved in integrating both elements into a metallosupramolecular assembly. In this work, we have designed a structurally optimized heteroleptic CrIII building block capable of binding rare earths. Following a complex-as-ligand synthetic strategy, two heterometallic supramolecular assemblies, in which three peripherical CrIII sensitizers coordinated through a molecular wire to a central ErIII or YIII, have been prepared. Upon excitation of the CrIII spin-flip states, the downshifted Er(4I13/2 → 4I15/2) emission at 1550 nm was induced through intramolecular energy transfer. Time-resolved experiments at room temperature reveal a CrIII → ErIII energy transfer of 62-73% efficiencies with rate constants of about 8.5 × 105 s-1 despite the long donor-acceptor distance (circa 14 Å). This efficient directional intermetallic energy transfer can be rationalized using the Dexter formalism, which is promoted by a rigid linear electron-rich alkyne bridge that acts as a molecular wire connecting the CrIII and ErIII ions.

Frequency Comb With High Tunability via Coexistence State Excitation and Cavity Modulation in Microelectromechanical Resonators

Frequency Comb With High Tunability via Coexistence State Excitation and Cavity Modulation in Microelectromechanical Resonators

(Invited) Blue Organic Light-Emitting Diode Using Dynamic Exciton for Low Driving Voltage

Among the three primary colors, blue emission in organic light-emitting diodes (OLEDs) are highly important but very difficult to develop. OLEDs have already been commercialized; however, blue OLEDs have the problem of requiring a high applied voltage due to the high-energy of blue emission. Herein, an ultralow voltage turn-on at 1.47 V for blue emission with a peak wavelength at 462 nm (2.68 eV) is demonstrated in an OLED device. This OLED reaches 100 cd/m2, which is equivalent to the luminance of a typical commercial display, at 1.97 V. Blue emission from the OLED is achieved by the selective excitation of the low-energy triplet states at a low applied voltage by using the charge transfer (CT) state as a precursor and the triplet-triplet annihilation, which forms one emissive singlet from two triplet excitons. We found that the essential component for efficient blue emission is a smaller energy difference between the CT state and triplet exciton, accelerating the energy transfer between the two states and achieving the optimal performance by avoiding direct decay from the CT state to the ground state. Our study demonstrates that the developed OLED allows for a much longer operation lifetime than that from a typical blue phosphorescent OLED because the blue emission originates from a stable low-energy triplet exciton that avoids degrading the constituent materials.

The dynamical evolution of exciton-polaritons in asymmetric ring-step potential well

The exciton-polariton, a quasi-particle formed by the coupling of excitons and photons, exhibits a semi-light-semi-matter nature, inheriting the advantages of both constituents and capable of achieving Bose-Einstein condensation at room temperature. This paper investigates the evolution of superposition states of semiconductor microcavity exciton-polariton Bose–Einstein condensate (BEC) within a ring-shaped structure. By employing theoretical modeling, the time-dependent dynamics of the superposition states of exciton-polaritons bound within a unique asymmetric ring-step potential well structure are analyzed, focusing on halide perovskite semiconductor materials. The study reveals correlations between the potential well structure of this step-like configuration and the transition of exciton-polariton BEC superposition states, shedding light on the evolution paths of BEC systems under specific structural influences and the fluctuation patterns of excitonic fields. These findings hold relevance for experimental manipulations of exciton-polariton superposition states within microcavities. This research demonstrates that ring-step potential well structures influence the excitation and evolution of exciton-polariton BEC superposition states, leading to transitions towards higher or lower order states. This transition is reflected macroscopically in alterations in the number and spatial distribution of interference petals in the superposition states. We consider initial states with orbital angular momentum quantum number l = 2, 3, 4, respectively. By exploiting the different structural relationships of ring-step potential wells, we achieve controlled evolutions of macroscopic occupation states, with interference petal numbers ranging from 4 to 6, 4–8, 6–8, 6–10, 8–10, 8–12, and 6–4.

Room temperature luminescence of 1,N2-etheno-2-aminopurine in poly (vinyl alcohol) films.

We studied spectral properties of 1,N2-etheno-2-aminopurine after immobilization in poly (vinyl alcohol) films. The absorption spectrum of 1,N2-ε2APu consists of two peaks centered at 300 and 370 nm, and the fluorescence spectrum has maximum at about 460 nm. The fluorescence quantum efficiency is 62%. The fluorescence anisotropy reaches a value of 0.3 at longer wavelengths, while it is low at shorter wavelengths (corresponding to the second single excited state). The 1,N2-ε2APu has a relatively long fluorescence lifetime of about 16 ns and a noticeable room temperature phosphorescence with a lifetime of about 220 ms. A broad phosphorescence emission band (425-675 nm) is centered at about 530 nm and markedly overlaps with fluorescence at shorter wavelengths. Surprisingly, the phosphorescence excitation spectrum of 1,N2-ε2APu-doped poly (vinyl alcohol) film differs from the absorption and fluorescence excitation spectra. The strongest room temperature phosphorescence excitation is about 335 nm. At longer excitation wavelengths, above 450 nm, where fluorescence cannot be excited, a triplet excitation is still possible. The 1,N2-ε2APu phosphorescence anisotropy spectra confirm direct triplet state excitation. The ability to excite molecules at long wavelengths can find applications in the study of biological molecules that are unstable when excited at high energies.

Photoisomerization of heptamethine cyanine (Cy7) dyes: A theoretical study

In this study, density functional theory (DFT) combined with time-dependent (TD) DFT calculations were employed to investigate the photoisomerization reaction kinetics of two near infrared (NIR) heptamethine cyanine (Cy7-NH3 and Cy7-SO3) dyes in the ground singlet state and the first excited singlet state. We found that the photoisomerization of the ground state all-trans Cy7 molecules results in at least one mono-cis and one all-cis species that demonstrate redshifted emission, in agreement with recently published transient state excitation modulation spectroscopy and fluorescence correlation spectroscopy measurements. The transition states were estimated for a whole photoisomerization pathway for both the ground singlet and first excited singlet state potential energy surfaces. We have found that all-cis isomers of the studied Cy7 dyes can be achieved through a sequential two-step photoisomerization within the excited singlet state potential energy surface, along the double CC bond adjacent to edge group (leading to mono-cis isomer 1) and along the double CC bond adjacent to the central-chain group (leading to mono-cis isomer 2). Computations show that all-trans→ mono-cis isomer 1→all-cis kinetics is limited by the first trans→ mono-cis isomer 1 stage, while the all-trans→ mono-cis isomer 2→all-cis pathway is limited by the second mono-cis isomer 2→all-cis stage. Accounting for the fact that mono-cis isomer 2 demonstrates red-shifted emission compared to the all-trans form and that this mono-cis isomer 2 is reachable through the energetically favorable all-trans→ mono-cis isomer 2 stage, we concluded that the experimentally observed red-shifted emission by Cy7-NH3 and Cy7-SO3 should be assigned to the formation of mono-cis isomer 2 species. If the all-cis isomer is populated through the double-step photoisomerization it can also be considered as a source of red-shifted emission. However, as follows from our simulations, the all-cis isomer is kinetically intricate to achieve compared to the mono-cis isomer 2.