Electronic Transition Energies Research Articles

Near-Infrared Room-Temperature Phosphorescence from Monocyclic Luminophores.

Compact luminophores with long emission wavelengths have aroused considerable theoretical and practical interest. Organics with room-temperature phosphorescence (RTP) are also desirable for their longer lifetimes and larger Stokes shifts than fluorescence. Utilizing the low electronic transition energy intrinsic to thiocarbonyl compounds, electron-withdrawing groups were attached to the 4H-pyran-4-thione core to further lower the excited state energies. The resulting mini-phosphors were doped into suitable polymer matrices. These purely organic, amorphous materials emitted near-infrared (NIR) RTP. Having a molar mass of only 162 g·mol-1, one of the phosphors emitted RTP that peaked at 750 nm, with a very large Stokes shift of 15485 cm-1 (403 nm). Thanks to the good processability of the polymer film, light-emitting diodes (LEDs) with NIR emission were easily fabricated by coating doped polymer on ultraviolet LEDs. This work provides an intriguing strategy to achieve NIR RTP using compact luminophores.

Near‐Infrared Room‐Temperature Phosphorescence from Monocyclic Luminophores

Compact luminophores with long emission wavelengths have aroused considerable theoretical and practical interest. Organics with room‐temperature phosphorescence (RTP) are also desirable for their longer lifetimes and larger Stokes shifts than fluorescence. Utilizing the low electronic transition energy intrinsic to thiocarbonyl compounds, electron‐withdrawing groups were attached to the 4H‐pyran‐4‐thione core to further lower the excited state energies. The resulting mini‐phosphors were doped into suitable polymer matrices. These purely organic, amorphous materials emitted near‐infrared (NIR) RTP. Having a molar mass of only 162 g·mol‐1, one of the phosphors emitted RTP that peaked at 750 nm, with a very large Stokes shift of 15485 cm‐1 (403 nm). Thanks to the good processability of the polymer film, light‐emitting diodes (LEDs) with NIR emission were easily fabricated by coating doped polymer on ultraviolet LEDs. This work provides an intriguing strategy to achieve NIR RTP using compact luminophores.

Exploring the influence of sudan IV Azo dye on the structural, optical, and dispersion characteristics of PVA/Su-IV composites

Flexible polymeric film composites consisting of polyvinyl alcohol (PVA) and Sudan IV azo dye (Su-IV) were synthesized using a casting method. Despite the known optical properties of PVA and azo dyes individually, the combined effects of Su-IV doping in PVA on the material’s optical and nonlinear optical properties have not been thoroughly investigated. This study addresses this gap by exploring the interactions between PVA and Su-IV at various doping concentrations (0.1–0.8 wt%) and their subsequent impact on the material’s structural and optical characteristics. Fourier transform infrared (FTIR) spectroscopy was employed to identify distinct vibrational groups within the composites, revealing that the incorporation of Su-IV induced random deviations in most absorption intensities compared to pristine PVA. Notably, new peaks at 519 and 444 cm−1 emerged, intensifying with increasing Su-IV concentrations, indicating significant interactions between the composite constituents. The optical properties were analyzed through transmittance and reflectance measurements, which uncovered new absorption peaks at 518 and 357 nm in PVA/Su-IV composites. These peaks correspond to electronic energy transitions of 2.4 and 3.6 eV, respectively, and their intensities increased with higher Su-IV content. Additionally, the indirect and direct bandgaps were decreased as Su-IV concentrations increased. The refractive index (n) analysis showed typical dispersion behavior between 850 and 2500 nm, aligning with the Wemple-DiDomenico (WDD) model. Furthermore, the oscillator parameters were calculated. Also, the nonlinear optical susceptibility (χ(3)) was boosted from 4.19 × 10−6 for pure PVA to 3.60 × 10−4 for the sample with 0.8 wt% Su-IV. The nonlinear refractive index (n2) was also measured at 8.55 × 10−2 for the doped sample. These findings demonstrate the potential of PVA/Su-IV composites for applications in nonlinear optics and photonics.

The stability, electronic and optical properties of nonmetal doped g-GaN: A first-principles calculation

Doping is an effective strategy to modulate the electronic performance of materials by forming new chemical bonds and relaxing the neighboring bonds, which may change catalytic performance of materials. Herein, we demonstrate the effects of a series of nonmetal (NM) dopants on the electronic properties and photocatalytic activity of g-GaN monolayer using first-principle calculations. NM dopants prefer to substitute N atom under Ga-rich condition. C, O and F doped specimens are highly stable under both Ga-rich and N-rich conditions. NM dopants induce the generation of impurity levels, contributing to reduce the electronic transition energies. S, Se and Te doped specimens increase by about 11, 8 and 4 times for absorption intensity in the region of visible light, respectively. Remarkably, S, Cl, Se, Br, Te and I dopants can effectively decrease the recombination rate of photogenerated electrons and holes of the g-GaN in photocatalytic reaction. H, B, C Si, P and As doped system can induce more active sites. Remarkably, halogen dopants could increase the both redox and reduction ability of g-GaN monolayer. Thus, NM dopants can effectively tune redox potential of g-GaN monolayer and improve its photocatalytic performance.

PAFerroptosis Combined with Metabolic Disturbance of Mito by p52-ZER6 for Enhanced Cancer Immunotherapy induced by Nano-Bacilliform-Enzyme.

The confused gene expressions and molecular mechanisms for mitochondrial dysfunction of traditional nanoenzymes is a challenge for tumor therapy. Herein, a nano-bacilliform-enzyme obtains the ability to inhibit p52-ZER6 signal pathway, regulate the genes related to mitochondrial metabolism, and possess the GOx/CAT/POD-like property. NBE acquires catalytic activity from the electronic energy transition. The tannin of NBE as a mitochondrial (Mito)-targeting guide overloads MitoROS, and then metabolic disorder and lipid peroxidation of Mito membrane occurs, thus leading to a novel death pathway called PAFerroptosis (pyroptosis, apoptosis, and Ferroptosis). Simultaneously, in order to refrain from mitophagy, hydroxychloroquine is mixed with NBE to form a combo with strength pyroptosis. As a result, NBE/combo improves the PAFerroptosis obviously by activation of CD8+T cells and inactivation of MDSC cells, up-regulating expression of caspase-3 signal pathway, intercepting DHODH pathway to arrive excellent antitumor effect (93%). Therefore, this study establishes a rational nanoenzyme for mitochondrial dysfunction without mitophagy for effective antitumor therapy.

The Photophysics and Photochemistry of Phenylalanine, Tyrosine, and Tryptophan: A CASSCF/CASPT2 Study.

Among all amino acids, the three aromatic systems including phenylalanine, tyrosine, and tryptophan are known to manifest UV light absorption at the higher wavelengths. Their fluorescent properties are important for protein detection and determination of the spatial structure. Based on ab initio quantum chemical calculations, the absorption spectra in the 0-12 eV UV range of these aromatic amino acids were interpreted, and the photochemistry of the lowest-lying excited states was studied. For that, molecular ground-state geometries were determined using both the coupled-cluster single and double (CCSD) and complete active space self-consistent field (CASSCF) methods. The vertical electronic transition energies, associated oscillator strengths, and electric dipole moments of the lowest excited states were computed at the CASPT2//CASSCF level. The decay mechanisms of the lowest-energy excited states were investigated by performing minimum energy path (MEPs) computations. The results showed that the CCSD and CASSCF computations yielded similar structures. The lowest-energy S1 state in phenylalanine and tyrosine, and S1 and S2 in tryptophan are mainly described by the π → π* excitation localized in the aromatic ring. Upon light absorption, the main photoresponse of the molecules is driven by the benzene, phenol, and indole chromophoric units.

Improving Photophysical Properties of Deazaflavin Derivatives by Acrylaldehyde Bridging: A Theoretical Investigation

AbstractThe electronic structure and photophysical properties of several acrylaldehyde‐bridged deazaflavin derivatives (cFLs) were investigated theoretically. The impact of acrylaldehyde bridging on photophysical properties of deazaflavin (cFL) is strongly site‐dependent. Specifically, the change of adiabatic energy of electronic transitions(ΔEad) and vibronic coupling promote fluorescent emission to be comparable to internal conversion of cFL and cFL4 (both C5−C6 and C9−N10 bridged, but C9−N10 bridged by propene), turning them eligible as fluorescent sensors. As El‐Sayed's rule is satisfied in cFL1(C5−C6 bridged), cFL2(C9−N10 bridged) and cFL3(both C5−C6 and C9−N10 bridged), intersystem crossing from first singlet excited state to triplet excited states (Tn) become dominant and the evolution of excited cFLs from T1 appears vital. The rate constants of photophysical processes indicate these cFLs are of dominantly high steady state T1 concentration and are potential triplet sensitizers. We expect the findings would pave the way for rational design of novel cFLs with extraordinary photophysical properties.

Fighting poison with poison: Degradation of ethyl paraben by Bi2Ti2O7-TiO2 doped with ethyl paraben

In this paper, a variety of titanium-bismuth-based composite photocatalysts were prepared by molecularly imprinted sol–gel method using ethyl paraben (EP) as the target pollutant and tetra-n-butyl titanate as the precursor for the degradation of EP. The photocatalytic removal of 81.4 % of 10 mg/L EP wastewater was achieved by synthesising Bi-EP-TiO2 for 30 min at 500°C, 5 g Bi and 2 g EP. The main component of the prepared Bi-EP-TiO2 and Bi-TiO2 is Bi2Ti2O7-TiO2. In addition, the forbidden bandwidth of Bi-EP-TiO2 is 0.28 eV larger than that of Bi-TiO2 but 0.30 eV smaller than that of TiO2, which suggests that, compared with TiO2, Bi-EP-TiO2 requires a lower electron-leap energy, which is capable of generating more. This suggests that Bi-EP-TiO2 requires lower electron transition energy than TiO2, and therefore can generate more photogenerated electron holes, thus improving the catalytic efficiency. Hence, Bi2Ti2O7-TiO2 doped with ethyl paraben degrades EP with excellent performance.

Reconciling mean-squared radius differences in the silver chain through improved measurement and ab initio calculations

Nuclear charge radius differences in the silver isotopic chain have been reported through different combinations of experiment and theory, exhibiting a tension of two combined standard errors. This study investigates this issue by combining high-accuracy calculations for six low-lying states of atomic silver with an improved measurement of the 5s2S1/2−5p2P3/2 transition optical isotope shift. Our calculations predict measured electronic transition energies in Ag at the 0.3% level, the highest accuracy achieved in this system so far. We calculate electronic isotope shift factors by employing analytical response relativistic coupled-cluster theory and find that a consistent charge radius difference between Ag107,109 is returned when combining our calculations with the available optical isotope shift measurements. We therefore recommend an improved value for the mean-squared charge radius difference between Ag107 and Ag109 as 0.207(6) fm2, within one combined error from the value derived from muonic Ag experiments, and an updated set of charge radii differences across the isotopic chain. Published by the American Physical Society 2024

Unravelling structural features of small molecules for photochemical transformation of environmental contaminants

Small molecules, including natural metabolites, organic matter decomposition products, and engineered oxidation byproducts, are widespread in aquatic environment. However, the limited understanding of the photochemical interactions of these small molecules with water pollutants hampers the development of effective environmental protection strategies. This study explores the structural features governing the photochemical transformation of toxic oxyanions by α- and β-dicarbonyl compounds. By integrating experimental observations with quantum chemical calculations, a robust correlation network was constructed. The correlation network reveals that the reactivity of small organic molecules with oxyanions could be quantitively predicted by their intrinsic properties, such as electronic transition energy, bond dissociation energy, molecular softness, molecular orbital gap, atomic charge, and molecular surface local ionization energy. This network maps the relationship between the molecular architecture of chemicals and their photochemical behaviors. This perspective offers fresh insights into the photochemical behaviors of small molecules in diverse environmental and chemical contexts and are helpful for developing advanced water treatment strategies toward a sustainable future.

Nuclear deformation effects in the spectra of highly charged ions

With the increasing precision of spectroscopic measurements, there is a growing demand for more accurate theoretical predictions, which requires the estimation of various higher-order effects, such as the nuclear deformation effect. Here, we present the results for nuclear deformation correction for the widest range of nuclei. The effects are investigated in terms of electronic transition energies, g factors, and hyperfine splitting constants, by implementing the deformed Fermi nuclear model to the Dirac equation. Based on the improved methodology and appropriate data classification, we present the results for over 1100 nuclei on figures, showing the general trends and anomalies. Moreover, it can serve as a simple tool providing estimations for specific planned research. In addition, we examine the connections and significance of deformation effects in the search of new physics with singly charged ions. Published by the American Physical Society 2024

Stacking Faults Enabled Second Harmonic Generation in Centrosymmetric van der Waals RhI3.

Second harmonic generation (SHG) in van der Waals (vdW) materials has garnered significant attention due to its potential for integrated nonlinear optical and optoelectronic applications. Stacking faults in vdW materials are a typical kind of planar defect that introduces a degree of freedom to modulate the crystal symmetry and resultant SHG response. However, the physical origin and tunability of stacking-fault-governed SHG in vdW materials remain unclear. Here, taking the intrinsically centrosymmetric vdW RhI3 as an example, we theoretically reveal the origin of stacking-fault-governed SHG response, where the SHG response comes from the energetically favorable AC̅ stacking fault of which the electrical transitions along the high-symmetry paths Γ-M and Γ-K in the Brillion zone play the dominant role at 810 nm. Such a stacking-fault-governed SHG response is further confirmed via structural characterizations and SHG measurements. Furthermore, by applying hydrostatic pressure on RhI3, the correlation between structural evolution and SHG response is revealed with SHG enhancement up to 6.9 times, where the decreased electronic transition energies and higher momentum matrix elements due to the stronger interlayer interactions upon compression magnify the SHG susceptibility. This study develops a promising foundation for nonlinear nano-optics applications through the strategic design of stacking faults.

Excited States in Single-Stranded and i-Motif DNA with Silver Ions.

We have studied the excited states and structural properties for the complexes of cytosine (dC)10 chains with silver ions (Ag+) in a wide range of the Ag+ to DNA ratio (r) and pH conditions using circular dichroism, steady-state absorption, and fluorescence spectroscopy along with the ultrafast fluorescence upconversion technique. We also calculated vertical electronic transition energies and determined the nature of the corresponding excited states in some models of the cytosine-Ag+ complexes. We show that (dC)10 chains in the presence of silver ions form a duplex stabilized by C-Ag+-C bonds. It is also shown that the i-motif structure formed by (dC)10 chains is destabilized in the presence of Ag+ ions. The excited-state properties in the studied complexes depend on the amount of binding ions and the binding sites, which is supported by the calculations. In particular, new low-lying excited states appear when the second Ag+ ion interacts with the O atom of cytosine in the C-Ag+-C pairs. A similar picture is observed in the case when one Ag+ ion interacts with one cytosine via the N7 atom.

Dynamic strain coupling driven by structural phase transition in mixed-dimensional 2H-MoS2/VO2 van der Waals heterointerfaces

Mixed-dimensional van der Waals (vdW) heterostructures, integrated two-dimensional (2D) atomic crystals with three-dimensional (3D) functional materials, offer a powerful means to manipulating physical properties and generating unprecedented functionalities. Understanding interfacial couplings at those hetero (homo)-interfaces is indispensable for exploring new optical and electronic devices. Herein, we investigated dynamically phase-transition-driven strain coupling across a vdW heterointerface through integrating 2D layered 2H-MoS2 nanoflakes onto 3D phase-change VO2 epitaxial thin films. The Raman peak positions of the in-plane and out-of-plane vibration modes E2g1 and A1g from the 2H-MoS2 nanoflakes show a phonon softening and reversible hysteresis loop as a function of temperature in this mixed-dimensional vdW 2H-MoS2/(1¯11)-VO2/(11¯02)-Al2O3 heterostructure, originating from the co-action of temperature-dependent anharmonicity in 2H-MoS2 and reversible structural phase transition (SPT)-induced in-plane tensile strain from the VO2 thin film. Accordingly, the integrated Raman scattering intensity of these two feature peaks of the 2H-MoS2 nanoflakes increased (decreased) as the temperature increased (decreased), exhibiting a hysteresis loop in the SPT and metal–insulator transition region of VO2. Additionally, the peak integrated intensity enhancement ratio of the E2g1 and A1g vibration modes was approximately 2.3 and 2.8, respectively. These results indicate that the dynamically SPT-driven in-plane tensile strain from the bottom VO2 layer interfacially couples with the adjacent 2H-MoS2 nanoflakes and results in a reduction in the electronic transition energy, leading to an enhancement in the Raman scattering intensity of 2H-MoS2. Our work holds promise for dynamic strain control of lattice dynamics and electron–phonon interaction of 2D materials for functional electronic and photoelectronic devices.

Electric-Tree Resistant Performance and Thermal Charge-Carrier Dissipation Mechanism of Voltage Stabilizer-Modified EPDM

In order to improve electric-tree resistant performance and dielectric breakdown strength of ethylene-propylene-diene misch-polymere (EPDM) material used for cable accessory reinforce insulation, the two specific aromatic ketone compounds—vinylphenylacetone (VPE) and 4-propylene oxyxy-2-hydroxydibenzenone (AOHBP) are employed as two paradigms of voltage stabilizer for chemical-graft modifications. Electric-tree resistances and insulation performances of modified EPDM materials and their charge trapping mechanism of thermoelectron inhibitions are studied by the accelerated electric-tree aging experiments, alternating current (AC) dielectric breakdown tests, surface potential trap-level analyses and first-principles calculations. Both the two species of voltage stabilizers are effective for promoting electric-tree inception voltage and dielectric breakdown strength, leading to a high extension of electric-tree morphology and smaller dimension of electric-trees growth, in which AOHBP is more significant. The two species of voltage stabilizers have been successfully grafted onto EPDM molecular-chains in thermal-chemistry crosslinking reactions of EPDM, introducing multiple shallow levels of charge traps, which reduces the energy released by trapping charge carriers and thus alleviates electric-tree aging of EPDM. The AOHBP and VPE represent a high electron affinity and a small electronic energy gap, which is competent of assimilating the kinetic energies of hot charge carriers whilst restricting Auger electronic excitation. Especially, the benzene group in voltage stabilizer renders shallow level charge traps with a larger carrier capture cross-section than deep traps and simultaneously possesses the high atomic vibration frequencies similar as electronic-transition energies, which results in effective dissipation on the kinetic energies of hot charge carriers. This mechanism dominates to increase electric-tree resistance and insulation strength of EPDM. The present study proves the important role of voltage stabilizers in improving insulation performance of EPDM material, and reveals the refrigeration mechanism on hot charge carriers for restricting electric-tree growth, which provides a significant strategy of chemical modifications for developing high-insulation cable accessory materials.

Bias-Tunable Quantum Well Infrared Photodetector.

With the rapid advancement of Artificial Intelligence-driven object recognition, the development of cognitive tunable imaging sensors has become a critically important field. In this paper, we demonstrate an infrared (IR) sensor with spectral tunability controlled by the applied bias between the long-wave and mid-wave IR spectral regions. The sensor is a Quantum Well Infrared Photodetector (QWIP) containing asymmetrically doped double QWs where the external electric field alters the electron population in the wells and hence spectral responsivity. The design rules are obtained by calculating the electronic transition energies for symmetric and antisymmetric double-QW states using a Schrödinger-Poisson solver. The sensor is grown and characterized aiming detection in mid-wave (~5 µm) to long-wave IR (~8 µm) spectral ranges. The structure is grown using molecular beam epitaxy (MBE) and contains 25 periods of coupled double GaAs QWs and Al0.38Ga0.62As barriers. One of the QWs in the pair is modulation-doped to provide asymmetry in potential. The QWIPs are tested with blackbody radiation and FTIR down to 77 K. As a result, the ratio of the responsivities of the two bands at about 5.5 and 8 µm is controlled over an order of magnitude demonstrating tunability between MWIR and LWIR spectral regions. Separate experiments using parameterized image transformations of wideband LWIR imagery are performed to lay the framework for utilizing tunable QWIP sensors in object recognition applications.

The LSU-Argonne conversion electron spectrometer: A new detector for the X-Array and SATURN decay station

A new conversion electron detector has been commissioned at the ATLAS/ CARIBU facility at Argonne National Laboratory. The LSU-Argonne Conversion Electron Spectrometer (LACES) is a LN2-cooled Si(Li) detector system designed to be incorporated into a decay station that comprises the dedicated HPGe clover array with a box geometry (X-Array) and the Scintillator and Tape Using Radioactive Nuclei (SATURN) device. This integration enables simultaneous measurements of conversion electrons and gamma-rays in decay experiments, yielding novel information on transition multipolarities, electric monopole transitions, and isomeric states that decay mostly via conversion electrons. A measurement of the energy resolution of LACES yielded 2.3-keV FWHM at 975 keV for electrons and 1.3-keV FWHM at 75 keV for X-rays. A detailed study of the absolute detection efficiency (at 5 mm from the source) was performed, where this quantity was determined experimentally in the range of electron transition energies between 25.5 keV and 1047.8 keV and subsequently simulated using the GEANT4 code. Measurement and simulations are found to be in excellent agreement. A precise characterization, for this type of detector system, of the absolute detection efficiency for such a wide energy range is reported for the first time.

The violet laser irradiation influence on the dispersive properties of the PVA/MO composite thick

Polyvinyl alcohol (PVA) polymer, methyl orange (MO) and their composite was dissolved in water in order to prepare films with different thickness by casting method. The films were irradiated by a violet laser with a wavelength 405 nm for different times (0, 10, 20, 30 and 40) minute. The dispersion parameters were calculated before and after exposure to the laser using the Wemple–DiDomenico method. Dispersion energy (E d) and the single oscillator energy of electronic transition (E o) were increased with increasing the irradiating time for PVA, MO and PVA/MO thick films. This is useful to modify geometrical and optical specifications for materials which has many applications especially in the medical field. The Urbach energy also can be controlled by the irradiation times since it decreased with increasing the laser irradiation time which can be used to enhance the structure of the material.

Ligand-Induced Intramolecular Redox Diversity in Titanium Complexes with Acenaphthene-1,2-diimine.

A series of the chlorido and alkoxychlorido titanium complexes of the general formula (dpp-Bian)Ti(OiPr)nCl3-n, where dpp-Bian = 1,2-bis[(2,6-iPr2C6H3)imino]acenaphthene n = 0 (2), 1 (3), 2 (4), as well as (dpp-Bian)Ti(OiPr)2 (5) and (dpp-Bian)Ti(OiPr)Cl3 (3-Cl), were isolated and characterized using single-crystal X-ray diffraction analysis and spectroscopic studies combined with density functional theory (DFT) calculations. In the solid state, compounds 2-4 reveal a square-pyramidal geometry at the metal center supported with monoanionic dpp-Bian, whereas 3-Cl with a neutral diimine ligand and 5 bearing a dianionic enebisamide dpp-Bian show, respectively, an octahedral and tetrahedral coordination surrounding the metal ion. Paramagnetic complexes 2-4 exhibit electron paramagnetic resonance spectra in both toluene solution and solid state, confirming the transfer of spin density from the metal ion to the dpp-Bian ligand as the number of alkoxy groups increases. The increase in polarity of the Ti-N bonds in the row 2 < 3 < 4 contributes to enhanced stability of the metal complexes with respect to O-donor molecules. Thus, in tetrahydrofuran (THF), compounds 2 and 3 undergo reversible solvolysis, whereas complex 4 is stable. The charge and spin density distributions as well as molecular orbital energies in 2-4 were analyzed on the basis of DFT calculations which also provided information on the electronic transition energies, absorption band assignments, and thermodynamic parameters of the reactions between the complexes and THF.

Solvatochromism, optical and electronic properties of thiosemicarbazone derivatives in solution phase

The electronic structure, solvatochromic and some optoelectronic properties of five different thiosemicarbazone (TSCs) derivatives with different substituents consisted from indole ring, benzyl ring and conjugated thiosemicarbazide have been investigated in detail. UV–vis. absorption spectra of TSC compounds have been analyzed in solvent media with different polarity. The spectral changes are observed to forming of solvent effects and substituents. Spectral behaviors and electronic transitions are interpreted based on the UV-Vis. spectra. Solvatochromic behaviors were defined by linear solvation energy relationships via multiple linear regression analysis by using Kamlet-Abboud-Taft and Catalán parameters. In addition, the correlations of electronic absorption transition energy with Marcus optical dielectric parameter and Reichardt-Dimroth parameter were also determined. Some optoelectronic parameters such as forbidden band gap energy and refractive index have been determined in different solvent medium. Thiosemicarbazone derivatives have a global electronic absorption transition energy of about 3.351 eV. According to LSER calculations, polarizability-induction of electronic transitions of the investigated molecules is effective. The (E)-4-(4-nitrobenzyl)-1-(2-oxo-2H-indol-3(3aH)-ylidene)thiosemicarbazide (TSC-B) compound that does not a methoxy group and contain nitro group substituent and has the highest forbidden energy range.