Small Energy Gap Research Articles

Realization of a Type-II Nodal-Line Semimetal in Mg3Bi2.

Nodal‐line semimetals (NLSs) represent a new type of topological semimetallic phase beyond Weyl and Dirac semimetals in the sense that they host closed loops or open curves of band degeneracies in the Brillouin zone. Parallel to the classification of type‐I and type‐II Weyl semimetals, there are two types of NLSs. The type‐I NLS phase has been proposed and realized in many compounds, whereas the exotic type‐II NLS phase that strongly violates Lorentz symmetry has remained elusive. First‐principles calculations show that Mg3Bi2 is a material candidate for the type‐II NLS. The band crossing is close to the Fermi level and exhibits the type‐II nature of the nodal line in this material. Spin–orbit coupling generates only a small energy gap (≈35 meV) at the nodal points and does not negate the band dispersion of Mg3Bi2 that yields the type‐II nodal line. Based on this prediction, Mg3Bi2 single crystals are synthesized and the presence of the type‐II nodal lines in the material is confirmed. The angle‐resolved photoemission spectroscopy measurements agree well with the first‐principles results below the Fermi level and thus strongly suggest Mg3Bi2 as an ideal material platform for studying the as‐yet unstudied properties of type‐II nodal‐line semimetals.

Three-particle electron-hole complexes in two-dimensional electron systems

Three-particle complexes consisting of two holes in the completely filled zero electron Landau level and an excited electron in the unoccupied first Landau level are investigated in a quantum Hall insulator. The distinctive features of these three-particle complexes are an electron-hole mass symmetry and the small energy gap of the quantum Hall insulator itself. Theoretical calculations of the trion energy spectrum in a quantizing magnetic field predict that, besides the ground state, trions feature a hierarchy of excited bound states. In agreement with the theoretical simulations, we observe new photoluminescence lines related to the excited trion states. A relatively small energy gap allows the binding of three-particle complexes with magnetoplasma oscillations and formation of plasmarons. The plasmaron properties are investigated experimentally.

Gold Nanoclusters Enhanced Photocatalytic Property of Bismuth Oxychloride

AbstractThis paper have synthesized bismuth oxychloride (BiOCl) nanoplate (BNS) by hydrothermal method and fabricated BiOCl‐gold nanoclusters (Au NCs) heterostucture nanomaterials (BANC) through electrostatic interaction. X‐ray diffraction, transmission electron microscope and X‐ray photoelectron spectroscopy characterizations indicate Au NCs successfully modified on BNS. The small energy gap makes Au NCs suitable for absorbing sunlight, while staggered energy bands between Au NCs and BiOCl could effectively separate electrons and holes, resulting in enhanced photocatlytic performance. Actually, under simulated sunlight irradiation, BANC could completely degrade rhodamine B within 30 minutes. In addition to this, the photostability test showed that the structure of BNAC did not changed after irradiation.

Nonadiabatic dynamics simulation method for transition metal complexes: Theory, developments, and applications

Excited-state related properties of transition metal complexes have received much attention in recent years due to their potential applications in the field of energy, material and biology. To fully understand the underlying mechanism, we always need to resort to ultrafast time-resolved spectroscopies as well as reliable ab initio nonadiabatic dynamics simulations. However, nonadiabatic dynamics simulation methods that are suitable for investigating excited-state dynamics of transition metal complexes still demand further developments to improve simulation efficiency and accuracy. In this short review, we have shortly present some recent developments of non-adiabatic dynamics methods that are suitable for investigating excited state properties of transition metal complexes, mainly including Multi-Configuration Time Dependent Hartree (MCTDH) and mixed quantum-classical surface hopping methods. In addition, we have introduced our recently developed TD-DFT-based generalized trajectory surface hopping method in which an efficient algorithm of computing nonadiabatic couplings is realized. In combination with the classical path approximation, this newly developed method can effectively simulate internal conversion and intersystem crossing processes of transition metal complexes on an equal footing. With this newly developed method, we have systematically investigated the early-time ultrafast excited-state dynamics of three Ir(III) complexes bearing distinct ligands. The ISC rates estimated by our simulations are 65, 81 and 140 fs, which agree quite well with experimentally measured ca. 80, 80 and 110 fs. These Ir(III) complexes show similar macroscopic phenomena, i.e., ultrafast IC and ISC, their microscopic excited-state relaxation dynamics are individually different, for example, electron and hole transfer dynamics. These new insights for excited-state dynamics of Ir(III) complexes could be helpful for rationally designing Ir-containing compounds with excellent photoluminescence performance. In addition, we have also investigated the ultrafast intersystem crossing process of Au(I) naphthalene derivatives. We have found that (1) ultrafast and sub-picosecond intersystem crossing processes are mainly caused by small energy gaps and large spin-orbit couplings between S1 and T n . (2) Adding the second gold(I)-phosphine group does not increase spin-orbit couplings between S1 and T n but decrease their values remarkably, which implies that heavy-atom effects are state-specific, not-universal. (3) The position at which the second gold(I)-phosphine group is attached has remarkable influence on electronic structures of S1 and T n and their relative energies, which affect energy gaps and spin-orbit couplings between S1 and T n and eventually modulate intersystem crossing rates from S1 to T n . This work exemplifies that different isomers of a compound could have distinct excited-state relaxation dynamics. Above simulation results not only agree pretty well with experiments, but also provide valuable insights into excited-state relaxation dynamics for these transition-metal-containing complexes. In one word, our present developments have established an efficient and accurate simulation tool for investigating excited-state dynamics of transition metal complexes.

Helium irradiated cavity formation and defect energetics in Ni-based binary single-phase concentrated solid solution alloys

Binary single-phase concentrated solid solution alloys (SPCSAs), including Ni80Co20, Ni80Fe20, Ni80Cr20, Ni80Pd20, and Ni80Mn20 (in atomic percentage), were irradiated with 200 keV He+ ions at 500 °C. He cavity size and density distribution were systematically investigated using transmission electron microscope. Here we show that alloying elements have a clear impact on He cavity formation. Cavity size is the smallest in Ni80Mn20 but the largest in Ni80Co20. Alloying elements could also substantially affect cavity density profile. In-depth examination of cavities at peak damage region (∼500 nm) and at low damage region (∼300 nm) demonstrates that cavity size is depth (damage) dependent. Competition between consumption and production of vacancies and He atoms could lead to varied cavity size. Density functional theory (DFT) calculations were performed to obtain the formation and migration energies of interstitials and vacancies. Combined experimental and simulation results show that smaller energy gap between interstitial and vacancy migration energies may lead to smaller cavity size and narrower size distribution observed in Ni80Mn20, comparing with Ni80Co20. The results of this study call attention to alloying effects of specific element on cavity formation and defect energetics in SPCSAs, and could provide fundamental understanding to predict radiation effects in more complexed SPCSAs, such as high entropy alloys.

5,14-Diaryldiindeno[2,1- f:1',2' -j]picene: A New Stable [7]Helicene with a Partial Biradical Character.

5,14-Diaryldiindeno[2,1- f:1',2' -j]picene (DDP, 1), a thermally and chemically stable helical arene, can be prepared from 1,4-bis[2-(arylethynyl)phenyl]benzene in four synthetic steps. Its helical backbone, which incorporates an o-quinodimethane moiety, was verified by X-ray crystallography, and this structural feature results in a very high barrier to racemization (exceeding 50 kcal/mol). DDP possesses versatile and promising properties, including a small HOMO-LUMO energy gap (1.31 eV for the dimesityl-substituted derivative 1ab), an electron spin resonance (ESR)-active character, a small triplet-singlet energy gap (4.75 kcal/mol), broad photoabsorption covering the ultraviolet, visible, and near-infrared (NIR) regions, two-photon absorption in the NIR range, and respectable ambipolar charge-transport behavior in a solution-processed organic field-effect transistor.

Structural Properties and Nonlinear Optical Responses of Halogenated Compounds: A DFT Investigation on Molecular Modelling

AbstractComputational chemistry is used to evaluate structures of different compounds by using principles of theoretical and quantum chemistry integrated into useful computer programs. It is used to determine energies, dipole moments and thermodynamic properties of different compounds. The present work reports the computational study of six donor-acceptor dyes. The computational method CAM-B3LYP with 6-31G(d,p) was used in this research to determine the effect of halogens on non-linear optical compounds. HOMO-LUMO energy gaps, dipole polarizabilities, first hyperpolarizabilities, and absorption spectra of six studied compounds (dye 1: 4-(2-(4-fluorophenyl)ethynyl)benzenamine; dye 2: 4-(2-(4-chlorophenyl)ethynyl)benzenamine; dye 3: 4-(2-(4-bromophenyl)ethynyl)benzenamine; dye 4: 5-(2-(4-fluorophenyl)ethynyl)benzene-1,2,3-triamine; dye 5: 5-(2-(4-chlorophenyl)ethynyl)benzene-1,2,3-triamine; dye 6: 5-(2-(4-bromophenyl)ethynyl)benzene-1,2,3-triamine) with aniline and halo phenyl segments were computed by using density functional theory (DFT) and time-dependent density functional theory (TDDFT). Results indicate that all dyes showed wavelengths of maximum absorbance in the visible region. Small HOMO-LUMO energy gaps were observed in all investigated dyes. The present calculations on these dyes (1-6) offer an understanding of the direction of charge transfer (CT) and how NLO behavior can be explained. The aniline-to-halo phenyl CT, caused by the combination of the donor amino group and the acceptor halo group, could be a reason for NLO behavior of these sorts of compounds. These compounds exhibit significant molecular second-order NLO responses, especially dyes (6) and (5), with second-order polarizability determined to be approximately 4600 a.u.

Optical spectroscopy and electrical analysis of La3+-doped PVA composite films for varistor and optoelectronic applications

Poly(vinyl alcohol), PVA, a matrix with 0, 0.185, 0.37, 1.85, 3.7 and 18.5 wt% of lanthanum (III) nitrate were synthesized by the traditional casting method. The order of the crystal structure and the interaction between the mixtures of the investigated materials were analyzed by X-ray and Fourier transform infrared (FT-IR) spectroscopies, while the Scanning Electron Microscopy (SEM), was used to study the surface images of them. Moreover, the optical filtering via UV/Vis/NIR spectroscopy, dielectric constant as well as the D.C. resistivity measurements that arose by the composite films with various wt% of La3+ ion were carried out. The structure study of these samples reveals that not only a cluster arises via La3+ ion on the SEM surface, but also, the semi-crystalline phases were confirmed by analyzing the pattern of the XRD and FT-IR. However, due to the complex formation of La3+ content in PVA matrix, there is an increment in the transitions strength, Ed, and the oscillator wavelength, λ0 as well as the index of refractions, while the band gap and the average excitation energy, Es, were decreased. Furthermore, there is a facility of moving charge carriers across the bands that contribute to the small energy gap via La3+-ion contents which clearly noticed in the dielectric and nonlinear I–V characteristics. The forward I–V measurement of the samples exhibited two distinct regions with different slopes, which is typical as nonlinear behavior for varistor with high applied voltage. Therefore, we can say that our samples have properties make them suitable to use in the applications of optoelectronic and varistor device.

Strategy for the Realization of Highly Efficient Solution-Processed All-Fluorescence White OLEDs-Encapsulated Thermally Activated Delayed Fluorescent Yellow Emitters.

Fabrication of highly efficient all thermally activated delayed fluorescence (TADF) white organic light-emitting diodes (WOLEDs) through solution-process still remains a big challenge. Here, two encapsulated TADF molecules with a small singlet-triplet energy gap (Δ EST) and high photoluminescence quantum yield (PLQY) were designed and synthesized as yellow emitters for solution-processed WOLEDs. The high current, power, and external quantum efficiencies of 41.6 cd A-1, 30.4 lm W-1, and 17.3% were achieved for the solution-processed all-fluorescence WOLEDs with a single-emission layer. In contrast, even with the same Δ EST and PLQY, the corresponding unencapsulated parent emitters will account for nearly 50% loss of the potential device efficiency. This is for the first time that the small molecular TADF blue host and TADF yellow guest are used to construct solution-processed all-fluorescence WOLEDs, which exhibit high efficiency comparable with most of the vacuum-deposited all-fluorescence white devices. These results not only demonstrate the great potential of TADF emitters in achieving highly efficient solution-processed WOLEDs, but also testify the key role of molecular encapsulation in reducing polar-exciton quenching and enhancing electroluminescence performance.

Theory of open quantum dynamics with hybrid noise

We develop a theory to describe dynamics of a non-stationary open quantum system interacting with a hybrid environment, which includes high-frequency and low-frequency noise components. One part of the system–bath interaction is treated in a perturbative manner, whereas the other part is considered exactly. This approach allows us to derive a set of master equations where the relaxation rates are expressed as convolutions of the Bloch–Redfield and Marcus formulas. Our theory enables analysis of systems that have extremely small energy gaps in the presence of a realistic environment. As an illustration, we apply the theory to the 16 qubit quantum annealing problem with dangling qubits (Dickson et al 2013 Nat. Commun. 4 1903) and show qualitative agreement with experimental results.

Superoctazethrene: An Open-Shell Graphene-like Molecule Possessing Large Diradical Character but Still with Reasonable Stability.

Laterally extended zethrenes can be regarded as Z-shaped nanographenes with four zigzag edges, but their synthesis is very challenging. Herein, we report the successful synthesis of by far the largest zethrene molecule, a superoctazethrene (SOZ) derivative SOZ-Cl, in crystalline form. Although the parent SOZ is calculated to have a very large diradical character ( y0 = 81.0%), SOZ-Cl shows reasonable stability ( t1/2 = 64 h under ambient conditions) and can be purified by silica gel column chromatography. It exhibits a small electrochemical energy gap ( Eg = 1.01 eV) and characteristics for open-shell singlet diradicaloids. Compared with a previously reported octazethrene derivative (OZ-TIPS), SOZ-Cl shows much larger diradical character ( y0 = 76.3% vs 43.4%) and smaller singlet-triplet gap (Δ ES-T = -2.30 kcal/mol vs -3.87 kcal/mol). Calculations also demonstrate global aromatic character of SOZ, but the smaller size octazethrene shows local aromaticity.

Dihedral Angle Control of Blue Thermally Activated Delayed Fluorescent Emitters through Donor Substitution Position for Efficient Reverse Intersystem Crossing.

This study shows a molecular design strategy for controlling the dihedral angle of two carbazole donors linked to a 2,4-diphenyl-1,3,5-triazine acceptor by a phenyl unit. Using this approach, six thermally activated delayed fluorescence emitters were synthesized with donors placed in various positions around a central phenyl core, and the photophysical relationship between the donor position and its dihedral angle was investigated. We demonstrate that this angle can affect both the strength of the charge transfer state and the conjugation across the entire molecule, effectively changing the singlet-triplet energy gap of the system. We conclude that materials containing two substituted -ortho donors or one -ortho and an adjacent -meta have the smallest energy gaps and the shortest delayed fluorescence lifetimes. On the other hand, emitters with no -ortho substituted donors have larger energy gaps and slow-to-negligible delayed fluorescence. When applying these materials to organic light-emitting diodes, these blue-emitting devices have a range of electrical properties, the best producing efficiencies as high as 21.8% together with high resistance to roll-off that correlate with the reverse intersystem crossing rates obtained.

Ultrafast Structure and Dynamics in the Thermally Activated Delayed Fluorescence of a Carbene-Metal-Amide.

Thermally activated delayed fluorescence has enormous potential for the development of efficient light emitting diodes. A recently discovered class of molecules (the carbene-metal-amides, CMAs) are exceptionally promising as they combine the small singlet-triplet energy gap required for thermal activation with a large transition moment for emission. Calculations suggest excited state structural dynamics modulate the critical coupling between singlet and triplet, but they disagree on the nature of those dynamics. Here we report ultrafast time-resolved transient absorption and Raman studies of CMA photodynamics. The measurements reveal complex structural evolution following intersystem crossing on the tens to hundreds of picoseconds time scale, and a change in the low-frequency vibrational spectrum between singlet and triplet states. The latter is assigned to changes in Raman active modes localized on the metal center.

Efficient donor-acceptor-donor borylated compounds with extremely small ΔEST for thermally activated delayed fluorescence OLEDs

Borane-based complexes have attracted considerable attention as thermally activated delayed fluorescence (TADF) emitters because of their thermal stability, high fluorescence efficiency, and favourable carrier mobility. In this work, we provide a facile way for borylated compounds to enable the spatially adjacent electron donor and acceptor groups to form a near-orthogonal configuration, generating an extremely small energy gap between triplet and singlet excited states (ΔEST, ∼30 meV). We demonstrate here a new series of donor-acceptor-donor borylated compounds using functional acridan derivatives as the electron donors and dimesitylborane as the acceptor moieties, which easily generates an intramolecular charge transfer upon excitation. All compounds achieved strong TADF emission and were used as dopants to fabricate TADF OLEDs. Yellow-emitting devices A and B yielded maximum efficiencies of 7.6% (22.2 cd/A) and 10.1% (32.2 cd/A), respectively. Moreover, the green-emitting device C achieved a maximum efficiency of 19.3% (56.8 cd/A) and subsequently dropped to 18.2% (53.6 cd/A) at luminance levels of 102 cd/m2. Overall, the high electroluminescent (EL) efficiencies, together with mitigated efficiency roll-off, illustrate that these compounds have a high potential for EL applications.

Synthesis, spectroscopic studies, DFT calculations, cytotoxicity and antimicrobial activity of some metal complexes with ofloxacin and 2,2′-bipyridine

Five new mixed ligand metal complexes were synthesized by the reaction of Zn(II), Zr(IV), Ce(III), Th(IV) and U(VI) with ofloxacin (HOfl) and 2,2′-bipyridine (Bipy) in presence of NaOH with 1:1:1:1 M ratio. The chelation possibility of the HOfl and Bipy towards metal ions has been proposed in the light of elemental analysis, molar conductance, spectral (mass, IR, UV–Vis. and 1H NMR), magnetic and thermal studies. Infrared spectra suggest that ligands interact with metal ions as bidentate. Electronic and magnetic data proposed the octahedral structure for all complexes. The experimental studies were complemented by quantum chemical calculation. DFT calculations were carried out and ΔE for compounds in LUMO and HOMO was evaluated and indicated that the U(VI) complex with small energy gap value ΔE (0.168eV), is more reactive than all complexes. The antimicrobial activity of the complexes against various microorganisms was tested and the in vitro anticancer activity against breast (MFC7) and Colon (HCT-116) cell lines was also screened.

Modeling of Anthocyanin Derivatives as Anti UV Agents

Molecular geometry optimization and electronic transition modeling of anti-UV activity on anthocyanin derivatives computationally have been carried out using the Hyperchem 8.0.10 application. Optimization of molecular geometry of anthocyanin compounds using a semi-empirical PM3 and ZINDO/s method with a gradient change of 0.01 kcal/(Å mol) for modeling the electronic transition of anthocyanin derivate. The results show that the transition type in 10 anthocyanin derivatives is n to π⃰ and π to π⃰ with anti UV activity in the UV-A and UV-C wavelength regions. Electron excitation for each anthocyanin derivative occurs in four molecular orbitals. The energy difference of HOMO-LUMO showed that malvidin compound was the one with the smallest energy gap, which was 5.61 eV and the luteolinidin compound was the one with the biggest energy gap, which was 5.94 eV.

Ab Initio Study on Electronic Structure of Some Imidazole Derivatives and Its Correlation with Corrosion Inhibition Properties

Imidazole and some of its derivatives have been known as a good candidate for corrosion inhibition application. In this study, ab initio calculation was carried out for several imidazole derivatives i.e. 2-phenylimidazole[1,2-α]pyridine, 6-methyl-2-phenylimidazole[1,2-α]pyridine, 6-methyl-2-(4-metoxyplenylimidazole)[1,2-α]pyridine, and 6-methyl-2-(4-chlorophenylimidazole)[1,2α]pyridine, in order to investigate their electronic properties as well as its correlation with their corrosion inhibition properties. Calculations were performed using Firefly software package with RHF method and 6-31G(d,p) basis set. Based on calculation results and analysis, it was found that 6-methyl-2-(4-metoxyphenylimidazole) [1,2α]pyridine compound has better potential as corrosion inhibitor than the rest of the compounds due to its small HOMO-LUMO energy gap, low ionization potential, low electron affinity, low electronegativity, and low global hardness i.e. 10.184 eV, 7.199 eV, -2.985 eV, 2.107 eV and 5.092 eV respectively. This compound also has the highest global softness (0.098 eV), while the greatest value of the dipole moment was owned by 6-methyl-2-(4-chlorophenylimidazole)[1,2α]pyridine with value of 6.125 Debye due to the existence of Cl atom that has larger polarity than the other substituents.

Magnetic Field-Sensitive Radical Pair Dynamics in Polymethylene Ether-Bridged Donor-Acceptor Systems.

Donor–acceptor systems forming exciplexes are versatile models for the study of magnetic field effects (MFEs) on charge recombination reactions. The MFEs originate from singlet–triplet interconversion within transient radical ion pairs (RIPs), which exist in a dynamic equilibrium with the exciplexes. Here, we describe the synthesis and MFEs of the chain-linked N,N-dimethylaniline (DMA)/9-methylanthracene (MAnt) donor–acceptor system MAnt–(CH2)n–O–CH2–CH2–DMA for n = 6, 8, 10, and 16. The MFEs are found to increase with increasing chain length. Effects as large as 37.5% have been observed for the long-chain compound with n = 16. The solvent dependence of the MFEs at magnetic field intensity 75 mT is reported. For the range of solvent static dielectric constants εs = 6.0–36.0, the MFEs go through a maximum for intermediate polarities, for which the direct formation of RIPs prevails and their dissociation and reencounter are balanced. Field-resolved measurements (MARY spectra) are reported for solutions in butyronitrile. The MARY spectra reveal that for n = 8, 10, 16, the average exchange interaction is negligible during the coherent lifetime of the radical pair. However, singlet–triplet dephasing broadens the lineshape; the shorter the linker, the more pronounced this effect is. For n = 6, a dip in the fluorescence intensity reveals a nonzero average exchange coupling of the order of ±5 mT. We discuss the field-dependence in the framework of the semiclassical theory taking spin-selective recombination, singlet–triplet dephasing, and exchange coupling into account. Singlet recombination rates of the order of 0.1 ns–1 and various degrees of singlet–triplet dephasing govern the spin dynamics. In addition, because of a small free energy gap between the exciplex and the locally excited fluorophore quencher pair, a fully reversible interconversion between the RIP, exciplex, and locally excited fluorophore is revealed by spectrally resolved MFE measurements for the long-chain systems (n = 10, 16).

Activation of Reactions in the Complex Region Using Microwave Irradiation.

Many mode-specific behaviors in the gas phase and at the gas-surface interface have been reported in the past decades. Infrared activation of a reagent vibrational mode is often used to study these reactions. In this work, an inexpensive and easily applied scheme using microwave irradiation is proposed for activating complex-forming reactions by transferring populations between closely spaced resonances. The important combustion reaction of H + O2 ↔ O + OH is used as a model system to demonstrate the feasibility of the proposed approach. The existence of a nonzero transition dipole moment matrix element between two highly excited resonance states separated by a small energy gap in the model system may allow one to use microwave irradiation to intervene and control the model reaction. The high energy resonance states of the model reaction can also release their energy by photon emission, which is in agreement with the experimentally observed chemiluminescence process.

Global Aromaticity in Macrocyclic Cyclopenta-Fused Tetraphenanthrenylene Tetraradicaloid and Its Charged Species.

A stable cyclopenta-fused tetraphenanthrenylene macrocycle, CPTP-M, was synthesized, and the structure was confirmed by X-ray crystallographic analysis. It exhibits a large radical character (number of unpaired electron, NU =3.52) and a small singlet-triplet energy gap (ΔES-T =-2.8 kcal mol-1 by SQUID). Its backbone contains 60 ([4n]) conjugated π electrons and is globally antiaromatic. NMR measurements and theoretical calculations revealed that its dication/dianion is globally aromatic owing to the existence of [4n-2]/[4n+2] π-conjugated electrons. Remarkably, the ring-current map of the tetraanion shows a unique ring-in-ring structure, with a diamagnetic outer ring and a paramagnetic inner ring. Accordingly, both the inner-rim and outer-rim protons are deshielded in its 1 H NMR spectrum. The tetraanion can be regarded as an isoelectronic structure of the known octulene, which shows similar electronic properties.