High Ionization Potential Research Articles

Formation of stable ionized complexes between coinage metal containing superhalogens and moderately reactive molecules: a DFT approach

The possibility of ionization of six moderately reactive molecules (Y), namely silicon dioxide (SiO2), ammonia (NH3), water (H2O), carbon dioxide (CO2), chloroform (CHCl3) and dichlorodifluoromethane (CCl2F2) by two properly chosen superhalogens (SHs), gold tetrafluoride (AuF4), and gold hexafluoride (AuF6) denoted as AuXn (n = 4 and 6) has been explored at density functional theory (DFT) level. With increasing electron affinity (EA) of superhalogen, its capability to oxidize molecules with higher ionization potential also increases. We have demonstrated that this competition between the electron-binding energy of the superhalogen system and the ionization potential (IP) of the molecule with which the superhalogen combines is a key factor to predict the stability and nature of the formed complex. Binding energies have been evaluated to predict the stability of the formed complexes. The charge flow between Y and AuXn and localization of spin density distribution on the Y molecules have been estimated to verify the nature of interaction between the two. Atom in molecule (AIM) analysis has been performed to predict the nature of the bonds formed between the two interacting species. Overall, our study gives a comprehensive idea about the nature and stability of the complexes formed when moderately reactive (or inert) molecules interact with superhalogens containing coinage metal.

Mixed dysprosium-lanthanide nitride clusterfullerenes DyM2N@C80-Ih and Dy2MN@C80-Ih (M = Gd, Er, Tm, and Lu): synthesis, molecular structure, and quantum motion of the endohedral nitrogen atom.

Systematic exploration of the synthesis of mixed-metal Dy-M nitride clusterfullerenes (NCFs, M = Gd, Er, Tm, Lu) is performed, and the impact of the second metal on the relative yield is evaluated. We demonstrate that the ionic radius of the metal appears to be the main factor allowing explanation of the relative yields in Dy-M mixed-metal systems with M = Sc, Lu, Er, and Gd. At the same time, Dy-Tm NCFs show anomalously low yields, which is not consistent with the relatively small ionic radius of Tm3+ but can be explained by the high third ionization potential of Tm. Complete separation of Dy-Gd and Dy-Er, as well as partial separation of Dy-Lu M3N@C80 nitride clusterfullerenes, is accomplished by recycling HPLC. The molecular structures of DyGd2N@C80 and DyEr2N@C80 are analyzed by means of single-crystal X-ray diffraction. A remarkable ordering of mixed-metal nitride clusters is found despite similar size and electronic properties of the metals. Possible pyramidalization of the nitride clusters in these and other nitride clusterfullerenes is critically analyzed with the help of DFT calculations and reconstruction of the nitrogen inversion barrier in M3N@C80 molecules is performed. Although a double-well potential with a pyramidal cluster structure is found to be common for most of them, the small size of the inversion barrier often leads to an apparent planar structure of the cluster. This situation is found for those M3N@C80 molecules in which the energy of the lowest vibrational level exceeds that of the inversion barrier, including Dy3N@C80 and DyEr2N@C80. The genuine pyramidal structure can be observed by X-ray diffraction only when the lowest vibrational level is below the inversion barrier, such as those found in Gd3N@C80 and DyGd2N@C80. The quantum nature of molecular vibrations becomes especially apparent when the size of the inversion barrier is comparable to the energy of the lowest vibrational levels.

Ligand stabilization of manganocene dianions - in defiance of the 18-electron rule.

Manganocene [Mn(C5H5)2], a 17-electron system, is expected to have a high electron affinity, as addition of an extra electron would make it a closed-shell 18-electron system. Surprisingly, it has a very low electron affinity of only 0.28 eV. Combined with its high ionization potential of around 7.0 eV, manganocene, therefore, should not be eager to either donate or accept an electron. We show that this property can be fundamentally altered with the proper choice of ligands, even though the total electron count remains the same. For example, the electron affinities of manganocene-derivatives Mn[C5(CN)5]2 and Mn[C5(BO)5]2, created by replacing H with CN or BO, are found to be 4.78 eV and 4.85 eV, respectively, making these species superhalogens. The power of the ligands is further demonstrated by studying the stability of their di-anions. Note that [Mn(C5X5)2]2- (X = H, CN, BO) di-anions, with 19-electrons, have one electron more than necessary to satisfy the 18-electron rule for stability. This factor, combined with the unavoidable repulsion between the two extra electrons, should destabilize [Mn(C5X5)2]2-. While that is the case for [Mn(C5H5)2]2-, we show that both Mn[C5(CN)5]22- and Mn[C5(BO)5]22- are stable against auto-detachment of the second electron by 0.7 eV and 0.38 eV, respectively. These results, based on first-principles calculations, demonstrate that ligand-manipulation can be used as an effective strategy to design and synthesize new materials with novel and tailored properties.

Center-line intensity of a supersonic helium beam

Supersonic helium beams are used in a wide range of applications, for example surface scattering experiments and, most recently, microscopy. The high ionization potential of neutral helium atoms makes it difficult to build efficient detectors. Therefore, it is important to develop beam sources with a high centre line intensity. Several approaches for predicting the centre line intensity exist, with the quitting surface model incorporating the largest amount of physical dependencies. However, until now only a limited amount of experimental data has been available. Here we present a study where we compare the quitting surface model with an extensive set of experimental data. In the quitting surface model the source is described as a sphere from where the particles leave in a molecular flow determined by Maxwell-Boltzmann statistics. We use numerical solutions of the Boltzmann equation to determine its properties. The centre-line intensity is then calculated using an analytical integral. This integral can be reduced to two cases, one which assumes a continuously expanding beam until the skimmer aperture, and another which assumes a quitting surface placed before the aperture. We compare the two cases to experimental data with a nozzle diameter of 10 micron, skimmer diameters ranging from 4 micron to 390 micron, a source pressure range from 2 to 190 bar, and nozzle-skimmer distances between 17.3 mm and 5.3 mm. To support the two analytical approaches, we have also performed equivalent ray tracing simulations. We conclude that the quitting surface model predicts the centre line intensity well for skimmers with a diameter larger than 120 micron when using a beam expanding until the skimmer aperture. For the case of smaller skimmers the trend is correct, but the absolute agreement not as good. We propose several explanations for this, and test the ones that can be implemented analytically.

High-triplet-level phthalimide based acceptors for exciplexes with multicolor emission

To provide high exciton utilization in organic light emitting diodes, phthalimide derivatives were designed and synthesized as exciplex-forming materials. Due to high triplet levels (2.92–3.11 eV) and ionization potentials (7.18–7.29 eV), the developed phthalimide derivatives were found to be not only appropriate accepting materials for the formation of different color exciplexes but also as bifunctional materials with a satisfactory hole and exciton-blocking abilities. Solid-state blends of the synthesized phthalimides as acceptors and a carbazole containing donors showed exciplex emission. Bimolecular blends exhibited multicolor exciplex emission which covered a visible spectrum from sky-blue to red colors, depending on the donor used. However, the photoluminescence quantum efficiencies of the studied exciplex-forming systems were found to be sensitive to the molecular design of the phthalimides. Acceptor with para-substituted phthalimide showed better exciplex-forming properties in comparison to other compounds. Exciplex-forming blend of (2-(4-benzoylphenyl)isoindoline-1,3-dione) as an acceptor and 1,3-di(9H-carbazol-9-yl)benzene (mCP) as a donor showed the most efficient sky-blue emission with small singlet-triplet splitting (0.06 ± 0.03eV). Such exciplex-forming molecular mixture was implemented as the light-emitting material in the sky-blue organic light emitting diodes which showed the brightness of 2500 cd m−2 and maximum external quantum efficiency of 2.9% due to the employment of both singlet and triplet excitons.

Approaching Standardless Quantitative Elemental Analysis of Solids: Microsecond Pulsed Glow Discharge and Buffer-Gas-Assisted Laser Ionization Time-of-Flight Mass Spectrometry.

Among various ionization sources for mass spectrometry, microsecond pulsed glow discharge (MP-GD) and buffer-gas-assisted laser ionization (BGA-LI) sources have the potential for direct quantitative elemental analysis of solids without the requirement of standard reference materials. The analytical potential of these two ionization sources has been evaluated by coupling them to orthogonal time-of-flight mass spectrometry (MS). A straightforward method was proposed to achieve the quantitative result: if a spectrum contains little interference and elemental peak currents are proportional to their concentrations, then the molar concentration of each element is equal to its ion current proportion in the total ion current. Two series of metal standards were applied for the evaluation. Explicit spectra with little interference can be acquired by both techniques. The interferences contribute only a very small portion to the total ion current for MP-GD-MS and BGA-LI-MS; therefore, their influence on the quantitative result can be ignored. All metal elements can be determined quite accurately by the proposed quantitation method, while gaps exist for nonmetal elements due to the high ionization potentials or gas species interference. Between the two techniques, BGA-LI-MS offers a more accurate quantitative result, primarily due to its higher plasma temperature.

Spectroscopic study of radical cation species formed on sulfated TiO2 upon benzene adsorption

Sulfated TiO2 is well known for its high acidity, which is due to the presence of sulfate ions that create strong Brönsted and Lewis acid sites. The Lewis acid sites can also exhibit oxidizing properties. As previously observed for sulfated ZrO2, the greater the strength of the acid site, the greater the oxidative potential.The oxidative ability can be evaluated by the interaction with a substance with high ionization potential such as benzene. Benzene was adsorbed on sulfated TiO2 at room temperature, and the species formed from the interaction was investigated by Raman and electron spin resonance (ESR) spectroscopy. Resonance Raman spectra of adsorbed benzene showed bands that are distinct from bands observed in the spectra of neutral molecules. Furthermore, from the absorption spectra in the visible and near-infrared it was possible to identify these species as phenylene oligomer radical cations. Also, aromatic radical cations were detected by ESR spectra. Although they were present in small amounts, these cations may be responsible for the bands observed in the Raman spectra because of the resonance Raman effect signal enhancement.

THE MORPHOLOGY FEATURES OF NANOSTRUCTURE OF ZIRCONIUM, MOLYBDENUM AND WOLFRAM OXIDES SYNTHESISED BY LASER ABLATION OF METALS IN WATER

The paper gives the investigation results of composition and morphology of oxide nanostructures of transition metals – zirconium, molybdenum and wolfram synthesized by laser ablation pure metals in water. High temperatures and pressures in zone of interaction of the pulse laser beam with the surface of metal in water contribute to the intensive synthesis of oxides in the form of clusters of particles with size about 1−2 nanometres. This is characteristic for metals with high ionization potential. As it follows from the data of X-ray diffraction analysis and scanning electron microscopy, specifically, the clusters are amorphous building material for nanostructures of the oxides of the metals enumerated above. The paper demonstrates the general pattern of their structure, namely, the stratification of the material from which the foam formations, thin-walled hollow round particles, plates, filaments, and other forms of nanostructures are composed. The research of morphological features of the nanostructures of zirconium, molybdenum and wolfram oxides obtained by the authors indicates that their use as substrates will achieve high gain values of Raman scattering ~ 10 4 −10 8 . In this range, there are the gain data previously obtained by the authors in the experiments on the synthesis of zirconium nano-oxides when using them as a substrate. This indicates that the nanostructures of molybdenum and wolfram nano-oxides also can serve as the effective substrates and can be used as a sensor in the high sensitive composition of substances analyzers based on surface enhanced Raman scattering.

Laser wakefield acceleration in Kr–He plasmas and its application to positron beam generation

We present the generation of quasi-monoenergetic electron beams via ionization injection in a laser wakefield acceleration by using a krypton–helium plasma. We obtained higher-energy electron beams of low divergence as compared with beams from the nitrogen–helium plasma at low plasma densities. This is attributed to an immediate ionization, trapping and acceleration of many electrons from several inner shells of the krypton atoms. On the other hand, there are very high ionization potentials of the K-shell nitrogen electrons which require the pulse (in our laser-plasma parameters) to experience a self-focusing (after 1.6 mm of propagation) at first before any ionization injection and acceleration of those two electrons per atom can occur. Based on those high-quality electron beams from the Kr–He plasmas, we generated ultra-relativistic positron beams with energies up to 100 MeV by placing a lead slab converter with a thickness of the order of its radiation length in the electron beam path after the gas jet. Experimental and Mont-Carlo simulated energy spectra of the positron beams are compared for the energy range of 30 MeV ≤ Ee+ ≤ 100 MeV along with the positron yields. In addition, various parameters of the positrons are investigated against the primary electron beam parameters. Such electron–positron cascading experiment could be helpful in future development for the composition of an all-optical electron–positron collider.

First-principles study of In mXn (X = Se, Te; m + n = 5 clusters: Structural, electronic, magnetic and spectral properties

Using the density functional theory (DFT) method, the geometrical structures of $ {\rm In}_{m}X_{n}$ ( $ X={\rm Se}$ , Te; $ m+n=5$ clusters are optimized, and their relative stability as well as electronic, magnetic and spectral properties are calculated. The ground state structures of $ {\rm In}_{m}X_{n}$ clusters are found to be largely similar for $ X={\rm Se}$ and Te, with the exception of $ {\rm In}_{2}X_{3}$ . The energy gap exhibits the maximum for $ {\rm In}_{2}{\rm Se}_{3}$ or $ {\rm In}_{3}{\rm Te}_{2}$ . The electronic properties of $ {\rm In}_{m}X_{n}$ clusters depend on their geometrical structures and, hence, on the value of m ; and $ {\rm In}_{2}{\rm Se}_{3}$ shows a low vertical electron affinity (VEA) of about 1.60eV and a high vertical ionization potential (VIP) of about 9.33eV. The total magnetic moment is 1 or 0μ_B for the clusters with $ m={\rm odd}$ (1, 3) or even (2, 4) , respectively. The local magnetic moments of X atoms amount to about 99.9% of the total magnetic moment, while those of In atoms are merely 0.1%. The IR and Raman spectra of $ {\rm In}_{m}X_{n}$ clusters exhibit similarity for $ X={\rm Se}$ and Te with an exception of $ {\rm In}_{2}X_{3}$ . The energies of the strongest peaks of $ {\rm In}_{m}{\rm Te}_{n}$ are largely smaller than the corresponding $ {\rm In}_{m}{\rm Se}_{n}$ in both IR and Raman spectra. For UV-Vis spectra, the absorption peaks at 200-400nm for all clusters and 390–780 nm for m = 1 and 3 (except $ {\rm In}_{3}{\rm Te}_{2}$ are likely to hint useful properties of UV and visible light absorption, respectively.

Extreme gaseous outflows in radio-loud narrow-line Seyfert 1 galaxies

We present four radio-loud NLS1 galaxies with extreme emission-line shifts, indicating radial outflow velocities of the ionized gas of up to 2450 km/s, above the escape velocity of the host galaxies. The forbidden lines show strong broadening, up to 2270 km/s. An ionization stratification (higher line shift at higher ionization potential) implies that we see a large-scale outflow rather than single, localized jet-cloud interactions. Similarly, the paucity of zero-velocity [OIII]$\lambda$5007 emitting gas implies the absence of a second narrow-line region (NLR) component at rest, and therefore a large part of the high-ionization NLR is affected by the outflow. Given the radio loudness of these NLS1 galaxies, the observations are consistent with a pole on view onto their central engines, so that the effects of polar outflows are maximized. In addition, a very efficient driving mechanism is required, to reach the high observed velocities. We explore implications from recent hydrodynamic simulations of the interaction between fast winds or jets with the large-scale NLR. Overall, the best agreement with observations (and especially the high outflow speeds of the [NeV] emitting gas) can be reached if the NLS1 galaxies are relatively young sources with lifetimes not much exceeding 1 Myr. These systems represent sites of strong feedback at NLR scales at work, well below redshift one.

A thermo-electrodynamic electric field dependent molecular ionization model to design electrical insulation system of HVDC wet-mate connectors under transient conditions

A powerful engineering software tool is elaborated to design proper dimensions/ systems/materials in a wet-mate DC connector under transient conditions. By using this tool, designers can examine various preventive measures to avoid streamer growth or limit it to only glow discharge in the oil portion of a wet-mate DC connector. In this regard, for a compact design of a wet-mate DC connector envisaged in this paper four mitigation methods including 1) using a dielectric solid covering the front portion of the moving contact, 2) increasing the relative permittivity of the dielectric solid, 3) using the dielectric oil with molecular constituents having high molecular ionization potentials, and 4) increasing the radius of curvature of the edge are evaluated.

Fe/O ratio behavior as an indicator of solar plasma state at different solar activity manifestations and in periods of their absence

We report the results of the investigation into plasma physical characteristics at various solar activity manifestations and in periods of their absence. These results have been obtained from quantitative estimates of the relative abundance of Fe/O ions in different energy ranges. Maximum values of the Fe/O ratio is shown to correspond to particle fluxes from impulsive flares for ions with energies <2 MeV/n (the most significant manifestation of the FIP effect). In particle fluxes from gradual flares, the Fe/O value decreases smoothly with ion energy and is noticeably inferior to values of fluxes in impulsive events. We have established that the properties of flares of solar cosmic rays indicate their belonging to a separate subclass in the total population of gradual events. Relying on variations in the abundance of Fe/O ions, we propose an xplanation of the solar plasma behavior during the development of flares of both classes. Magnetic clouds (a separate type of coronal mass ejections (CME)), which have regions of turbulent compression and are sources of strong geomagnetic storms, exhibit a relative composition of Fe ions comparable to the abundance of Fe in ion fluxes from gradual flares. We have found out that the Fe/O value can be used to detect penetration of energetic flare plasma into the CME body at the initial phase of their joint development and to estimate its relative contribution. During solar minimum with complete absence of sunspots, the Fe/O ratio during periods of “quiet” solar wind show absolutely low values of Fe/O=0.004–0.010 in the energy range from 2–5 to 30 MeV/n. This is associated with the manifestation of the cosmic ray anomalous component, which causes an increase in the intensity of ion fluxes with a high first ionization potential, including oxygen (O), and elements with a low first ionization potential (Fe) demonstrate weakening of the fluxes. As for particles with higher energies (Ek>30 MeV/n), the Fe/O increase is due to the decisive influence of galactic cosmic rays on the composition of impurity elements in the solar wind under solar minimum conditions. The relative content of heavy elements in galactic cosmic rays 30–500 MeV/n is similar to values in fluxes from gradual flares during high solar activity. During solar minimum without sunspots, the behavior of Fe/O for different ion energy ranges in plasma flows from coronal holes (CH) and in the solar wind exhibits only minor deviations. At the same time, plasma flows associated with the disturbed frontal CH region can be sources of moderate geomagnetic storms.

Поведение отношения Fe/O как показателя состояния солнечной плазмы при различных проявлениях активности и в периоды ее отсутствия

We report the results of the investigation into plasma physical characteristics at various solar activity manifestations and in periods of their absence. These results have been obtained from quantitative estimates of the relative abundance of Fe/O ions in different energy ranges. Maximum values of the Fe/O ratio is shown to correspond to particle fluxes from impulsive flares for ions with energies <2 MeV/n (the most significant manifestation of the FIP effect). In particle fluxes from gradual flares, the Fe/O value decreases smoothly with ion energy and is noticeably inferior to values of fluxes in impulsive events. We have established that the properties of flares of solar cosmic rays indicate their belonging to a separate subclass in the total population of gradual events. Relying on variations in the abundance of Fe/O ions, we propose an xplanation of the solar plasma behavior during the development of flares of both classes. Magnetic clouds (a separate type of coronal mass ejections (CME)), which have regions of turbulent compression and are sources of strong geomagnetic storms, exhibit a relative composition of Fe ions comparable to the abundance of Fe in ion fluxes from gradual flares. We have found out that the Fe/O value can be used to detect penetration of energetic flare plasma into the CME body at the initial phase of their joint development and to estimate its relative contribution. During solar minimum with complete absence of sunspots, the Fe/O ratio during periods of “quiet” solar wind show absolutely low values of Fe/O=0.004–0.010 in the energy range from 2–5 to 30 MeV/n. This is associated with the manifestation of the cosmic ray anomalous component, which causes an increase in the intensity of ion fluxes with a high first ionization potential, including oxygen (O), and elements with a low first ionization potential (Fe) demonstrate weakening of the fluxes. As for particles with higher energies (Ek>30 MeV/n), the Fe/O increase is due to the decisive influence of galactic cosmic rays on the composition of impurity elements in the solar wind under solar minimum conditions. The relative content of heavy elements in galactic cosmic rays 30–500 MeV/n is similar to values in fluxes from gradual flares during high solar activity. During solar minimum without sunspots, the behavior of Fe/O for different ion energy ranges in plasma flows from coronal holes (CH) and in the solar wind exhibits only minor deviations. At the same time, plasma flows associated with the disturbed frontal CH region can be sources of moderate geomagnetic storms.

Ab initio study of structural and electronic properties of SinC5-nH8 (n = 0–5) series: Probing the 2D to 3D structural transition

Abstract In this study, we studied the structural and electronic properties in the Si n C 5 - n H 8 (n = 0–5) series using ab initio calculations. We performed global minimum and low-lying isomers search for the C5H8, Si C 4 H 8 , Si 2 C 3 H 8 , Si 3 C 2 H 8 , Si 4 CH 8 and Si 5 H 8 stoichiometries at the B3LYP/3-21G level of theory. The lowest isomers were recalculated at the CCSD(T)/CBS//B3LYP/6-311++G∗∗ level of theory. It was shown that Si 2 C 3 H 8 structure is more stable than the other structures with high ionization potential and HOMO-LUMO energy gap. We also showed the 2D-3D that transition, which occurs only at n = 3, is due to stronger C–C σ bonds compared to weaker C–Si and Si–Si σ bonds. The results were found in good agreement with available experimental findings.

Electronic structure of phosphorene nanoflakes. A theoretical insight

Abstract Phosphorene nanoflakes of different shapes and sizes were studied at the hybrid BHandHLYP level of theory. This functional accurately reproduces the experimental bond lengths and valence angles of black phosphorus. All nanoflakes were found to have a singlet ground state and their band gaps (Egs) decrease linearly with 1/N, where N is the number of P atoms in the nanoflakes. It seems that the topology of the nanoflake edges does not affect Eg. The ionization potentials (IPs) and electron affinities (EAs) generally grow smaller with increasing nanoflake size. The change in IPs and EAs with size correlate with the delocalization pattern of polaron cations and anions. The shape and nature or the longest edge (zig-zag or armchair) affect both the IP and EA. Nanoflakes with a long zigzag edge have higher IPs and lower EAs compared to square systems. Low theoretically calculated hole reorganization energies (less than 0.1 eV) are in agreement with the experimentally determined high hole mobility in phosphorene. The low hole reorganization energies are due to the better ability of phosphorene nanoflakes to delocalize polaron cations compared to polaron anions.

8.0% Efficient all-polymer solar cells based on novel starburst polymer acceptors

The polymer N2200, with its π-conjugated backbone composed of alternating naphthalene diimide (NDI) and bithiophene (DT) units, has been widely used as an acceptor for all-polymer solar cells (all-PSCs) owing to its high electron mobility and suitable ionization potential and electron affinity. Here, we developed two naphthalene diimide derivatives by modifying the molecular geometry of N2200 through the incorporation of a truxene unit as the core and NDI-DT as the branches. These starburst polymers exhibited absorption spectra and molecular orbital energy levels that were comparable to N2200. These copolymers were paired with the wide-bandgap polymer donor PTzBI-O to fabricate all-polymer solar cells (all-PSCs), which displayed impressive power conversion efficiencies up to 8.00%. The improved photovoltaic performances of all-PSCs based on these newly developed starburst acceptors can be ascribed to the combination of increased charge carrier mobilities, reduced bimolecular recombination, and formation of more favorable film morphology. These findings demonstrate that the construction of starburst polymer acceptors is a feasible strategy for the fabrication of high-performance all-PSCs.

Factors Influencing the Potency of Alzheimer Inhibitors: Computational and Docking Studies.

Density functional theory (B3LYP/6-31G [d]) is performed to study the effect of molecular and electronic structures of the investigated β-secretase 1 (BACE1) Alzheimer's inhibitors on their biological activities and discuss the correlation between their inhibition efficiencies and quantum chemical descriptors. IC50 values of the investigated compounds are mostly affected by the substituted R2 phenyl moiety. The calculations show that the presence of electron withdrawing group increases the half maximal inhibitory concentration (IC50). Structure-activity relationship studies show that the electronic descriptors, energy of high occupied molecular orbital, ΔE, lipophilicity, hardness, and ionization potential index, are the most significant descriptors for the correlation with IC50. Molecular docking simulation is performed to explain the mode of interaction between the most potent drug and the binding sites of the BACE1 target. A good correlation between the experimental and the theoretical data confirms that the quantum chemical methods are successful tools for the discovery of novel BACE1 drugs.

Electrochemical measurements and theoretical studies for understanding the behavior of catechol, resorcinol and hydroquinone on the boron doped diamond surface.

Using electrochemical techniques (cyclic voltammetry (CV) and differential pulse voltammetry (DPV)) with a boron-doped diamond (BDD) electrode it was possible to study the behavior of hydroquinone (HQ), catechol (CT) and resorcinol (RS), in aqueous solutions as well as to associate the electrochemical profiles with computational simulations. It led to understanding the factors that influence the direct electrooxidation of HQ, CT and RS on the BDD surface. Theoretical calculations demonstrated that the compounds with lower HOMO energy and high ionization potential (IP) are more stable, showing a higher Epa, denoting that HOMO energies and IP are related to the difficulty of oxidizing (losing an electron) a specific compound. Analyzing the electro-oxidation reactions of HQ, CT and RS by using computational calculations, it was possible to verify the reversibility behavior, direct oxidation pathway and the possible intermediates formed during electron-transfer. The results clearly demonstrated that the reversibility was attained for HQ and CT, while this behavior is not feasible, thermodynamically speaking, for RS and this was confirmed by DFT calculations. For direct oxidation mechanisms, HQ and CT are quickly oxidized, but RS produces stable intermediates. These experimental and theoretical results also explain the behavior when the compounds were analyzed by electroanalytical techniques, suggesting that the interactions by direct electron-transfer determine the stability of response (sensitivity) as well as the limit of detection. The results are described and discussed in light of the existing literature.

π-Bridge modification of thiazole-bridged DPP polymers for high performance near-IR OSCs.

Thiophene-bridged and thiazole-bridged diketopyrrolopyrrole (DPP) polymers for near-infrared (near-IR) photovoltaic applications have been investigated via density functional theory (DFT) and Marcus charge transfer theory. Compared with thiophene-bridged DPP polymers, thiazole-bridged polymers have higher ionization potentials (IPs) but poorer optical absorption and worse charge transport capability. Different beneficial substituents replaced the hydrogen atoms (H) on the thiazole rings for the sake of reversing the disadvantages of thiazole-bridged DPP polymers and making these compounds better near-infrared absorbing materials. In order to gain deep insight into the impact of π-bridge modification on the photoelectronic properties of DPP polymers, their electronic structures, absorption capabilities, intramolecular charge transfer properties and charge transport performances have been analyzed. The calculated results reveal that π-bridge modification is a feasible way to improve the light-absorbing capability, electron excitation properties and charge transport performance of thiazole-bridged DPP polymers. It is expected that π-bridge modification can also work for other polymers containing π-bridge units. We hope that our research efforts will be helpful in the designing of new near-IR absorbing materials and could motivate further improvement of organic solar cells.