Excited State Transitions Research Articles

Characterizing the Lipkin-Meshkov-Glick model excited-state quantum phase transition using dynamical and statistical properties of the diagonal entropy.

Using the diagonal entropy, we analyze the dynamical signatures of the Lipkin-Meshkov-Glick model excited-state quantum phase transition (ESQPT). We first show that the time evolution of the diagonal entropy behaves as an efficient indicator of the presence of an ESQPT. We also compute the probability distribution of the diagonal entropy values over a certain time interval and we find that the resulting distribution provides a clear distinction between the different phases of ESQPT. Moreover, we observe that the probability distribution of the diagonal entropy at the ESQPT critical point has a universal form, well described by a beta distribution, and that a reliable detection of the ESQPT can be obtained from the diagonal entropy central moments.

The role and growth of strain – reducing layer by molecular -beam epitaxy in a multi – stack InAs/(In,Ga)As sub - monolayer quantum dot heterostructure

Abstract The present study focuses on a growth strategy to achieve a uniform (and larger) dot size distribution in a multi-stack InAs/InGaAs sub-monolayer (SML) quantum dot (QD) heterostructure by capping with a varying InxGa1-xAs (x = 0.15) layer thickness (Y). The InxGa1-xAs layer serves both as matrix medium for the dot growth and strain - reducing layer (SRL) to preserve the QD morphology from decomposition. The dots capped by an optimum SRL or capping layer (CL) thickness will alleviate from dot segregation or intermixing, surface diffusion and dot inhomogeneity effects, thus paving way to grow a nearly defect - free quantum dot heterostructure. The experimental calculations on low – temperature (19 K), high – excitation power (1.1 kW/cm2) photoluminescence (PL) revealed ground – state (GS) emission energies at 1.12, 1.14, 1.09 eV for 2, 4, and 6 ML SRL thickness respectively. While, the presence of QD excited state (ES) transitions has been analysed using PL - excitation (PLE) spectroscopy, as the CL will highly alter the band offsets as well as strain inside QDs. The interfacial structural quality, strain relaxation in QDs due to SRL was inspected through high-resolution X – ray diffraction (HRXRD) and Raman measurements. The self – consistent Schrodinger – Poisson solver based on 8 – band k.p formulation was used to evaluate the PL energy and strain profile as a comparison to experimental data. Hence, the sample containing 2 ML CL thickness showed superior results in terms of PL emission and strain, which leads towards the growth of uniform QDs for photodetector (PD) applications operating in the short – wave infrared (SWIR) regime (λ: 0.9 μm–2.5 μm, Energy: 1.377 eV - 0.495eV).

Electronically Excited States of Closed-Shell, Cyano-Functionalized Polycyclic Aromatic Hydrocarbon Anions

Few anions exhibit electronically excited states, and, if they do, the one or two possible excitations typically transpire beyond the visible spectrum into the near-infrared. These few, red-shifted electronic absorption features make anions tantalizing candidates as carriers of the diffuse interstellar bands (DIBs), a series of mostly unknown, astronomically ubiquitous absorption features documented for over a century. The recent interstellar detection of benzonitrile implies that cyano-functionalized polycyclic aromatic hydrocarbon (PAH) anions may be present in space. The presently reported quantum chemical work explores the electronic properties of deprotonated benzene, naphthalene, and anthracene anions functionalized with a single cyano group. Both the absorption and emission properties of the electronically excited states are explored. The findings show that the larger anions absorption and emission energies possess both valence and dipole bound excitations in the 450–900 nm range with oscillator strengths for both types of >1×10−4. The valence and dipole bound excited state transitions will produce slightly altered substructure from one another making them appear to originate with different molecules. The known interstellar presence of related molecules, the two differing natures of the excited states for each, and the wavelength range of peaks for these cyano-functionalized PAH anions are coincident with DIB properties. Finally, the methods utilized appear to be able to predict the presence of dipole-bound excited states to within a 1.0 meV window relative to the electron binding energy.

Elaborating the influence of substituent on energy gap and spin-orbit coupling of singlet-triplet excited states of novel organic light-emitting anthraquinone compounds in solution

In this work, we presented a theoretical investigation of single-triplet excited state transition process by the energy gap (ΔEST) and spin-orbit coupling (SOC) for a series of novel designed anthraquinone compounds in solution. The molecular conformation, steady-state spectra and molecular orbitals were performed by quantum chemistry calculations to investigate the substituent effects on the ΔEST and SOC and single-triplet state transition process. The molecular conformation gradually change from the planar of the ground state to torsion, which reduced the orbital overlap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO). It was further demonstrated that the ΔEST and SOC remarkably depend on substituents with different conjugation and the presence of benzene in the donor units in solution. The change of ΔEST from 1.80 eV to 0.70 eV and SOC from 0.495 cm−1 to 5.127 cm−1. Furthermore, it was confirmed that the presence of benzene ring and the enhancement of conjugation in the donor substituent can reduce the ΔEST and enhance the SOC in different anthraquinone compounds. This work paves a way for an understanding of the single-triplet excited state transition process controlled by ΔEST and SOC characters of these kinds of anthraquinone compounds in solution.

Guiding synthetic targets of anodically coloring electrochromes through density functional theory.

Electrochromic devices offer many technological applications, including flexible displays, dimmable mirrors, and energy-efficient windows. Additionally, adsorbing electrochromic molecular assemblies onto mesoporous metal-oxide surfaces facilitates commercial and manufacturing potential (i.e., screen-printing and/or roll-to-roll processing). These systems also demonstrate synthetic versatility, thus making a wide array of colors accessible. In this work, using Time-Dependent Density Functional Theory (TD-DFT), we investigated ten different bi-aryl type molecules of 3,4-ethylendioxythiophene (EDOT) conjugated to various phenyl derivatives as potential anodically coloring electrochromes (ACEs). The non-substituted phenylene, hexylthiol-EDOT-phenyl-phosphonic acid, PA1, was synthesized and characterized as a means of model validity. PA1 absorbs in the UV region in its neutral state and upon oxidation absorbs within the visible, hence showcasing its potential as an ACE chromophore. The properties of PA1 inspired the designs of the other nine structural derivatives where the number and position of methoxy groups on the phenylene were varied. Using our DFT treatment, we assessed the impact of these modifications on the electronic structures, geometries, and excited-state properties. In particular, we examined stabilization intermolecular interactions (S-O and O-H) as they aid in molecule planarization, thus facilitating charge transport properties in devices. Additionally, destabilizing O-O forces were observed, thereby making some chromophores less desirable. A detailed excited state analysis was performed, which linked the simulated UV-Vis spectra to the dominant excited state transitions and their corresponding molecular orbitals. Based on these results, the nine chromophores were ranked ergo providing an ordered list of synthetic targets.

TD-DFT and Experimental Methods for Unraveling the Energy Distribution of Charge-Transfer Triplet/Singlet States of a TADF Molecule in a Frozen Matrix.

Reverse intersystem crossing (RISC) rate of a thermally activated delayed fluorescence (TADF) molecule is sensitive to the energy alignment of the singlet charge-transfer state (1CT), triplet charge-transfer state (3CT), and locally excited triplet state (3LE). However, the energy distribution of the charge-transfer states originating from the conformational distribution of TADF molecules in a solid matrix inevitably generated during the preparation of a solid sample due to the rotatable donor-acceptor linkage is rarely considered. Moreover, the investigation of the energy distribution of the 3CT state is both theoretically and experimentally difficult due to the triplet instabilities of time-dependent density functional (TD-DFT) calculations and difficulties in phosphorescence measurements, respectively. As a result, the relationships between conformational distribution, configurations of excited state transition orbitals, and excited state energies/dynamics have not been clearly explained. In this work, we determined the energy distribution of CT states of the TADF emitter TPSA in frozen toluene at 77 K by the measurement of time-resolved spectra in the full time range (1 ns to 30 s) of emission including prompt fluorescence, TADF, 3CT phosphorescence, and 3LE phosphorescence. We obtained the energy band of CT states where 1CT and 3CT states are distributed in the range of 2.85-3.00 and 2.64-2.96 eV, respectively. We tested various global hybrid and long-range corrected functionals for the TD-DFT calculation of 3CT energy of TPSA and found that only the M11 functional shows consistent results without triplet instability. We performed TD-DFT with the M11* functional optimized for a robust dihedral angle scan of 3CT states without triplet instability and reproduced the energy band structure obtained from the experiment. Through TD-DFT and experimental investigations, it is estimated that the dihedral angles of donor-acceptor (θD-A) and acceptor-linker (θA) of TPSA in frozen toluene lie within the range 70° ≤ θD-A ≤ 90° and 0° ≤ θA ≤ 30° respectively. Our results show that the dihedral angle distribution must be considered for further investigation of the photophysics of TADF molecules and the development of stable and efficient TADF emitters.

Excited-state vibration-polariton transitions and dynamics in nitroprusside

Strong cavity coupling to molecular vibrations creates vibration-polaritons capable of modifying chemical reaction kinetics, product branching ratios, and charge transfer equilibria. However, the mechanisms impacting these molecular processes remain elusive. Furthermore, even basic elements determining the spectral properties of polaritons, such as selection rules, transition moments, and lifetimes are poorly understood. Here, we use two-dimensional infrared and filtered pump–probe spectroscopy to report clear spectroscopic signatures and relaxation dynamics of excited vibration-polaritons formed from the cavity-coupled NO band of nitroprusside. We apply an extended multi-level quantum Rabi model that predicts transition frequencies and strengths that agree well with our experiment. Notably, the polariton features decay ~3–4 times slower than the polariton dephasing time, indicating that they support incoherent population, a consequence of their partial matter character.

Tuning spin–orbit coupling in (6,5) single-walled carbon nanotube doped with sp3 defects

Single-walled carbon nanotubes (SWCNTs) containing sp3 defects are a promising class of optoelectronic materials with bright photoluminescence and demonstrated single-photon emission. Using density functional theory simulations, complemented by measurements, we investigate the electronic structure of a series of quantum defects attached to (6,5) SWCNT with the goal of tuning the spin–orbit coupling by introduction of a heavy atom in the defect structure. We characterize the ground state electronic and spin properties of four synthesized and three potential defects on the tube and find that all of the synthesized defects considered introduce a localized midgap defect-centered state containing a single electron, ≈0.2–0.3 eV above the valence band. The spin density is located at the sp3 defect site with negligible spin–orbit coupling even with the presence of a Pd atom. Three additional functional groups were tested via computation to increase spin localization near the metal, thereby increasing spin–orbit coupling. We predict that only the chlorodiphosphanepalladium(II)– [Cl(PH3)2Pd(II)–] defect results in increased spin–orbit splitting of the defect state and the conduction band associated with the pristine-like SWCNT, a measure of the spin–orbit coupling of excited state transitions. This study suggests that for unpassivated sp3 defects in (6,5) SWCNT, forming a direct bond between a heavy atom and the sp3 carbon allows for tuning of spin–orbit coupling.

A novel experimental method in connecting the trans- and gauche-states of Ethanol to high accuracy using synchrotron radiation spectrum through torsionally excited state transitions

In this report the initial results of a breakthrough and novel method to energetically connect the lowest-lying trans- (e0) and the gauche- (e1 and o1) states of Ethyl Alcohol. It is well known that the transitions between the trans- and gauche states in the ground internal rotational levels for OH torsion are forbidden due to symmetry considerations. This presented a considerable challenge to model the Hamiltonian for this molecule on a global basis and the most successful model required these two states to be treated separately as if the trans- and gauche- states represent two different molecules. The present communication reports for the very first time the method to energetically connect the trans- sub-states and the gauche sub-states with experimental accuracy. This would open a new vista to theoretical spectroscopists for a global model with both types of symmetry. The novel method has been conceived recently with the availability of high-resolution far-infrared (FIR) with very little noise. The spectroscopic idea behind the approach is presented here using a few representative states in the form of a rapid publication. The details are in progress and will be commutated in a future report.

Увеличение эффективности тандема полупроводниковый лазер-оптический усилитель на основе самоорганизующихся 8s квантовых точек

The rate equations are used to analyze the characteristics of a tandem consisting of a laser diode and a semiconductor optical amplifier made of a single heterostructure with quantum dots. The optimal value of the current distribution coefficient the amplifier and the laser, as well as the optimal resonator length that provides the highest output power of the tandem were determined. It is shown that the use of the tandem allows, at the same total consumed current, to significantly (more than 4 times for 1 A) increase the power emitted through the ground-state optical transition in comparison with that achievable with a laser diode solely being limited by the onset of lasing through an excited-state optical transition.

Assessment of the performance of DFT functionals in the fulfillment of off-diagonal hypervirial relationships.

Off-diagonal hypervirial relationships, combined with quantum mechanical sum rules of charge-current conservation, offer a way to test electronic excited-state transition energies and moments, which does not need any external reference. A number of fundamental relationships were recast into absolute deviations from zero, which have been used to assess the performance of some popular DFT functionals. Extended TD-DFT calculations have been carried out for a pool of molecules chosen for this purpose, adopting a large basis set to ensure high quality results. A partial agreement with previous benchmarks is observed.

Superuniversality from disorder at two-dimensional topological phase transitions

We investigate the effects of quenched randomness on topological quantum phase transitions in strongly interacting two-dimensional systems. We focus first on transitions driven by the condensation of a subset of fractionalized quasiparticles (`anyons') identified with `electric charge' excitations of a phase with intrinsic topological order. All other anyons have nontrivial mutual statistics with the condensed subset and hence become confined at the anyon condensation transition. Using a combination of microscopically exact duality transformations and asymptotically exact real-space renormalization group techniques applied to these two-dimensional disordered gauge theories, we argue that the resulting critical scaling behavior is `superuniversal' across a wide range of such condensation transitions, and is controlled by the same infinite-randomness fixed point as that of the 2D random transverse-field Ising model. We validate this claim using large-scale quantum Monte Carlo simulations that allow us to extract zero-temperature critical exponents and correlation functions in (2+1)D disordered interacting systems. We discuss generalizations of these results to a large class of ground-state and excited-state topological transitions in systems with intrinsic topological order as well as those where topological order is either protected or enriched by global symmetries. When the underlying topological order and the symmetry group are Abelian, our results provide prototypes for topological phase transitions between distinct many-body localized phases.

Rotational spectroscopy and precise molecular structure of 1,2-dichlorobenzene

Supersonic expansion rotational spectroscopy at 4–18 GHz with rectangular pulse and chirp excitation was used to measure spectra of twelve isotopic species of 1,2-dichlorobenzene at conditions of completely resolved double chlorine hyperfine structure by using a newly constructed slit expansion nozzle. Four species: 37Cl13 and the three singly substituted 13C species have been assigned for the first time. Spectroscopic constants for six isotopic species with single deuterium substitution were considerably improved by using chemically synthesised samples. Hyperfine constants in the field gradient principal axes system were determined and used as a test of self-consistency of the analysis. Additional room-temperature measurements up to 275 GHz allowed assignment of rotational transitions in first excited states of the three lowest normal modes. The determined values of vibrational changes in rotational constants, inertial defects, and quartic and sextic centrifugal distortion constants, allowed calibration of harmonic and anharmonic force field calculations, resulting in determination, among others, of precise semi-experimental equilibrium, reSE, geometry of 1,2-dichlorobenzene. It is found that r(C-C) and ∠(C-C-C) in the phenyl ring of 1,2-dichlorobenzene show very small changes relative to benzene.

Deep learning for UV absorption spectra with SchNarc: First steps toward transferability in chemical compound space.

Machine learning (ML) has shown to advance the research field of quantum chemistry in almost any possible direction and has also recently been applied to investigate the multifaceted photochemistry of molecules. In this paper, we pursue two goals: (i) We show how ML can be used to model permanent dipole moments for excited states and transition dipole moments by adapting the charge model of Gastegger et al. [Chem. Sci. 8, 6924-6935 (2017)], which was originally proposed for the permanent dipole moment vector of the electronic ground state. (ii) We investigate the transferability of our excited-state ML models in chemical space, i.e., whether an ML model can predict the properties of molecules that it has never been trained on and whether it can learn the different excited states of two molecules simultaneously. To this aim, we employ and extend our previously reported SchNarc approach for excited-state ML. We calculate UV absorption spectra from excited-state energies and transition dipole moments as well as electrostatic potentials from latent charges inferred by the ML model of the permanent dipole moment vectors. We train our ML models on CH2NH2 + and C2H4, while predictions are carried out for these molecules and additionally for CHNH2, CH2NH, and C2H5 +. The results indicate that transferability is possible for the excited states.

Steady-state and time-resolved upconversion photoluminescence in Yb3+-Er3+ co-doped transparent ceramics of YAG.

Transparent ceramics (TCs) represent a new family of functional hard materials. In this Letter, steady-state and time-resolved upconversion photoluminescence in Yb3+-Er3+ co-doped TC of yttrium aluminum garnet (TC-YAG) are reported for the first time, to the best of our knowledge. Under the excitation of near-infrared 940 nm laser at room temperature, the Yb3+-Er3+ co-doped TC-YAG emits intense multi-color luminescence consisting of cyan, green, and red groups of sharp lines. More excitingly, the green group of luminescence due to the transitions from 4S3/2 to 4I15/2 states of Er3+ are the prominent components with the average lifetime of ∼0.3ms. The internal quantum efficiency of the green luminescence is estimated to be 32.8%. A unique dual-resonance energy transfer from Yb3+ to Er3+ via the excited-state vibronic transitions is proposed as the principal mechanism of the strongest green luminescence of Er3+ ions in TC-YAG.

Nd3+ doped magnesium zinc sulfophosphate glass: New candidate for up-conversion solid state laser host

Abstract Phosphate based glasses with neodymium ions (Nd3+) doping are advantageous for high energy short pulse up−conversion (UC) solid−state laser applications. In this work, the magnesium zinc sulfophosphate glass systems with composition of (60−x)P2O5–20MgO–20ZnSO4−xNd2O3 (where x = 0.0, 0.5, 1.0, 1.5 and 2.0 mol%) were prepared via melt−quenching method. Structures of as−quenched samples were characterized at room temperature using Fourier-transform infrared spectrometer FTIR and Raman measurements. Thermogravimetry−differential thermal analyses (TG−DTA) confirmed the thermal stability (>100 °C) of selected glasses. Ultraviolet–visible near-infrared (UV–Vis–NIR) absorption and photoluminescence (PL) spectroscopy were used to evaluate the optical properties of the proposed glasses. Absorption spectra of glasses revealed thirteen characteristic bands in the range of 328–875 nm which were assigned to the ground state to various excited states transitions in Nd3+ ions. The reliability of the Judd−Ofelt (JO) evaluation was authenticated via the attainment of the very low value of root mean square deviation (0.18 × 1020 to 0.63 × 1020 cm2). The spectroscopic quality factors of glasses were enhanced from 1.51 to 2.07 with the increase in Nd3+ ions doping contents. Glass containing 1.5 mol% of Nd3+ ions displayed a slight reduction of Ω2 value, validating the improvement of symmetrical environment around Nd3+ ions in the glass network. Meanwhile, the observed enhancement in the Ω4 and Ω6 values with increasing Nd3+ ions content was ascribed to the improvement of glass viscosity and rigidity. The achieved green−yellowish PL band around 580 nm (emerged from 2G7/2 → 4I9/2 transition) exhibited large branching ratio (83–84%), indicating efficient lasing transition with improved emission cross−section (3.25–4.70 × 10−25 m2) in the glass system. Based on results, the proposed glass system was effective to be used in UC solid−state laser applications.

New ^{13}C(α,n)^{16}O Cross Section with Implications for Neutrino Mixing and Geoneutrino Measurements.

Precise antineutrino measurements are very sensitive to proper background characterization. We present an improved measurement of the ^{13}C(α,n)^{16}O reaction cross section which constitutes significant background for large ν[over ¯] detectors. We greatly improve the precision and accuracy by utilizing a setup that is sensitive to the neutron energies while making measurements of the excited state transitions via secondary γ-ray detection. Our results shows a 54% reduction in the background contributions from the ^{16}O(3^{-},6.13 MeV) state used in the KamLAND analysis.

First limits on double beta decays in ^mathbf{232}Th

As one of the primordial radioactive isotopes, ^{232}mathrm{Th} mainly undergoes alpha -decay with a half-life of 1.402cdot 10^{10} years. However, it is also one of 35 double beta decay candidates in which the single beta -decay is forbidden or strongly suppressed. 181 mg of thorium contained in a gas mantle were measured in a HPGe well-detector at the Gran Sasso Underground Laboratory with a total exposure of 3.25 gtimes d.We obtain half-life limits on all double beta decay modes of ^{232}mathrm{Th} to excited states of ^{232}mathrm{U} on the order of 10^{11-15} years. For the most likely transition into the 0^+_1 state we find a lower half-life limit of 6.7cdot 10^{14} years (90% C.I.). These are the first constraints on double beta decay excited state transition in ^{232}mathrm{Th}.

Complex Density of Continuum States in Resonant Quantum Tunneling

We introduce a complex-extended continuum level density and apply it to one-dimensional scattering problems involving tunneling through finite-range potentials. We show that the real part of the density is proportional to a real "time shift" of the transmitted particle, while the imaginary part reflects the imaginary time of an instantonlike tunneling trajectory. We confirm these assumptions for several potentials using the complex scaling method. In particular, we show that stationary points of the potentials give rise to specific singularities of both real and imaginary densities which represent close analogues of excited-state quantum phase transitions in bound systems.

Mesons and Glueballs, the Strong Effective Coupling within Analytic Confinement

The phenomena of hadron mass generating, strong running coupling and radiative transitions of charmonium excited states have been studied in the framework of a relativistic field model with analytic confinement. A meson mass equation is derived and a specific new behavior of the mass-dependent strong coupling $$\mathop {\bar {\alpha }}\nolimits_s $$ is revealed in the time-like region. A new infrared fixed point $$\mathop {\bar {\alpha }}\nolimits_s (0) = 1.032$$ has been found at origin. Independent and new estimates on the scalar glueball mass, radius and gluon condensate value have been performed. The spectrum of conventional mesons have been calculated by introducing a minimal set of parameters with relative errors less than 1.8 percent compared to the latest data. Accurate estimates of the leptonic decay constants of pseudoscalar and vector mesons have also been performed. Partial decay widths of the dominant radiative transitions of the charmonium orbital excitations have been estimated with reasonable accuracy.