Ionization Potential Research Articles

Theoretical Rotational and Vibrational Spectral Data for the Hypermagnesium Oxide Species Mg2O and Mg2O.

While magnesium is astronomically observed in small molecules, it largely serves as a contributor to silicate grains, though how these grains form is not well-understood. The smallest hypermagnesium oxide compounds (Mg O/Mg O ) may play a role in silicate formation, but little vibrational reference data exist. As such, anharmonic spectroscopic data are computed for Mg O, Mg O, and Mg O using quartic force fields (QFFs). Explicitly-correlated coupled-cluster QFFs for the neutral species perform well, implying that full multireference treatment may not be necessary for such systems if enough electron correlation is included. Equation-of-motion ionization potential (EOMIP) methods for Mg O QFFs circumvent previous symmetry breaking issues even in explicitly-correlated coupled-cluster results, motivating the need for EOMIP treatments at minimum for such systems. All three species are found to have high-intensity vibrational frequencies. Even so, the highly intense frequency ( Mg O: 894.7 cm-1/11.18 μm; Mg O: 915.0 cm-1/10.91 μm) for either neutral state may be astronomically obscured by the polycyclic aromatic hydrocarbon 11.2 μm band. Mg O may be less susceptible to such obfuscation, and its intensity is computed to be a massive 4793 km mol-1.

On the Ionization Energy of the Atomic Gold Ion Au2+

On the Ionization Energy of the Atomic Gold Ion Au2+

Mechanistic investigation and machine learning exploration of structure-activity relationship of NHC-Mn catalyzed ester hydrosilylation reaction

This study aims to deeply investigate the mechanism of NHC-Mn catalyzed ester hydrosilylation reaction and the impact of different ligands on reaction activity through the comprehensive application of DFT calculations and machine learning technologies. We initially proposed four possible reaction mechanisms including two radical mechanisms and two 2e mechanisms. Then calculate the potential energy surfaces of them. It was demonstrated through calculations that the radical mechanisms were implausible, while the 2e outer-sphere mechanism was proven to be reasonable. A detailed analysis of the Si–H bond activation step in different reaction mechanisms highlighted the crucial role of steric effects in the process. Furthermore, the rate-determining step in the 2e mechanism (outer-sphere), the hydride transfer process, was also thoroughly studied. Eventually, a predictive model was successfully constructed using machine learning methods, which is a model based on the Ridge algorithm with 17 features that accurately predict the impact of different types of ligands on the reaction barrier. Analysis of the model revealed important factors affecting reaction activity, such as the vertical ionization potential of the metal hydride intermediate, the charge on the metal hydride, and the bond order of the Mn–H bond.

First-principles Calculation of Cumene: Molecular Structure, Electronic Structures, Spectroscopic Analysis, and Thermodynamic Properties

This study uses the DFT method for the investigation of optimized structure, electronic structures, charge analysis, FT-IR, FT-Raman spectroscopic analysis and thermodynamic properties. The optimized energy and dipole moment are 9531.775 eV and 0.3818 Debye. The bond lengths of C1-C2 and C1-H7 molecules inside the benzene ring are observed to be 1.39 Å and 1.08 Å respectively. The bond angle of C1-C2-C3 and C2-C1-C6 are found to be 120.10 Å and 119.36 Å. The HOMO-LUMO energy gap is 6.331 eV which corresponds very close to the energy gap of 6.321 eV obtained from density of states. The global parameters with ionization energy value 6.747 eV, electron affinity with 0.4152 eV, chemical potential with -3.5811 eV, electronegativity with 3.5811 eV, global hardness with 3.1659 eV, softness with 0.3148 eV-1 and electrophilicity index with 2.0253 eV are obtained. The Mulliken charges analysis indicate that most of the carbon atoms except C4 and C12 are found to carry negative charges where all of the H-atoms are found having positive charge. The molecular electrostatic potential, electrostatic potential and electron density identify different electrophilic and nucleophilic region and its reactive natures. The FT-IR spectroscopy shows strong C-H vibrations at 3186-3093 cm-1, methyl group vibration at 3091-3078 cm-1 and the ring vibrations at 1641-1482 cm-1. The heat capacity at constant volume and at constant pressure, internal energy, enthalpy, entropy increase with increasing temperature. However, Gibb’s free energy shows opposite nature providing very important insights according to the change in temperature.

Enhanced electrical insulation properties of 2-isopropenyl-2-oxazoline grafted polypropylene for high voltage direct current power cables

Polymers have been extensively used for high voltage direct current transmission systems as insulation power cables. Space charge accumulation consistently remains the primary factor contributing to the degradation of the electrical insulation properties of polymers. Grafting modification is a valid approach for suppressing the injection of space charges and free electrons by inducing deep traps. In this paper, the modified polypropylene grafted the group with low ionization energy is reported. The deep traps are revealed by the thermally stimulated depolarization current experiment and the band structure as well as the electrostatic potential by density functional theory simulation. The method with the innovative hybrid functional and basis set is adopted to establish the average local ionization distribution of the grafting group, thus confirming its strong electrophilicity. Furthermore, the modified polypropylene has been proved to obtain higher breakdown strength and operational stability by experiments. This work can provide insights for the design and selection of power cables with excellent electrical insulation properties.

DFT studies on N-(1-(2-bromobenzoyl)-4-cyano-1H-pyrazol-5-yl)

In this work, molecular descriptors of N-(1-(2-bromobenzoyl)-4-cyano-1H-pyrazol-5-yl) halogenated benzamides (1a-h) have been computed using a quantum chemical technique through DFT. Prior work involved the synthesis of compounds (1a-h) and the assessment of their anticancer activity on breast, colon, and liver tumors: MCF-7, HCT-116, and HepG-2 cell lines respectively. Since 1a, 1b, and 1d showed the most potential anticancer impact, their ability to inhibit EGFRWT was investigated. Based on the biological data, 1b inhibited EGFRWT the most. According to the docking evaluation, an H-bond with the threonine residue was one of the main non-covalent contacts between 1b and the EGFRWT active site residues. PES, MESP, HOMOs, LUMOs, energy band gap, global reactivity indices [electron affinity (A), ionization energies (I), electrophilicity index (ω), nucleophilicity index (ε), chemical potential (μ), electronegativity (χ), hardness (η), and softness (S)], condensed Fukui functions, NBO, and NCIs are the molecular descriptors of 1a-h that were computed using DFT technique. According to the theoretical investigation results, compounds (1a-h) might have anticancer effects; these findings are consistent with the biological findings from our previous research. Compound 1b had the lowest binding energy, according to an assessment of the binding energies between the threonine and the three most active compounds (1a, 1b, and 1d). This is consistent with the outcomes of the docking study and the biological examination of the influence of 1a, 1b, and 1d on EGFRWT.

Investigation of corrosion inhibition and adsorption properties of quinoxaline derivatives on metal surfaces through DFT and Monte Carlo simulations

Abstract This work presents a multiscale theoretical investigation into the potential of quinoxaline derivatives (Q1–Q6) as corrosion inhibitors for various metals (Fe(110), Cu(111), and Al(110)). Employing a combined approach combining density functional theory (DFT) and Monte Carlo simulations, we explore the relationship between molecular structure, electronic properties, and adsorption behavior. Density functional theory (DFT) and molecular dynamics simulations (MDS) were used to investigate the electronic characteristics of diverse compounds. The study included key parameters including highest occupied molecular orbital energy (E HOMO), lowest unoccupied molecular orbital energy (E LUMO), energy gap (E g) between E LUMO and E HOMO, dipole moment, global hardness, softness (σ), ionization energy (I), electron affinity (A), electronegativity (χ), back-donation energy E b−d, global electrophilicity (ω), electron transfer, global nucleophilicity (ε), and total energy (sum of electronic and zero-point energies). These properties, alongside adsorption energies (following the trend Q6 > Q2 > Q3 > Q4 > Q5 > Q1), are used to identify promising inhibitor candidates and establish structure–property relationships governing their effectiveness. The results suggest that inhibitor efficiency increases with a decreasing energy gap between frontier orbitals. Notably, the protonated state of Q6 exhibits high reactivity, low stability, and strong adsorption, making it a potential candidate for further exploration. This comprehensive theoretical approach offers crucial insights for the conceptual development of new and powerful corrosion inhibitors.

Surface structure-based model to calculate thermal and optical properties in nanoscale and quantum dot semiconductors

Surface combination structure was used to design the construction of nano and quantum films, particles, and dots. The created model was applied to tetrahedral semiconductor nanoparticles and quantum dots with a successful performance. It works better than reported experimental data across the whole size range, from the bulk state to the critical size of quantum dots. The model helps to figure out the melting point that changes with the nanosize scale as applied on Si and Sn, which are simple tetrahedral semiconductors, and for CdS and CdSe, which are among II-VI group compounds. It was also used to calculate melting-related parameters such as cohesive energy, Debye temperature, vibrational entropy, and melting enthalpy. The nanosize dependence of the lattice volume and the atom's ionization energy describes the solid surface structure. From the model, an equation was obtained to calculate the energy gaps in Si, CdS, and CdSe particles that are nano- and quantum-dot-sized, and the results are compared to the experimental data that goes with these particles.

Wide-energy programmable microwave plasma-ionization for high-coverage mass spectrometry analysis

Although numerous ambient ionization mass spectroscopy technologies have been developed over the past 20 years to address diverse analytical circumstances, a single-ion source technique that can handle all analyte types is still lacking. Here, a wide-energy programmable microwave plasma-ionization mass spectrometry (WPMPI-MS) system is presented, through which MS analysis can achieve high coverage of substances with various characteristics by digitally regulating the microwave energy. In addition, ionization energy can be rapidly scanned using programmable waveforms, enabling the simultaneous detection of biomolecules, heavy metals, non-polar molecules, etc., in seconds. WPMPI-MS performs well in analyzing real samples, rapidly analyzing nine toxicological standards in one drop of serum, and demonstrating good quantification and liquid chromatography coupling capability. The WPMPI-MS has also been used to detect soil extracts, solid pharmaceuticals, and landfill leachate, further demonstrating its robust analytical capabilities for real samples. The prospective uses of the technology in biological and chemical analysis are extensive, and it is anticipated to emerge as a viable alternative to commercially available ion sources.

Determination and study of correlations of relative sensitivity factors in metal and metal oxide samples by glow discharge mass spectrometry

The determination of relative sensitivity factor (RSF) plays a crucial role in achieving accurate quantitative analysis in glow discharge mass spectrometry (GD-MS). In this study, the RSF of typical elements in 14 metal and metal oxide matrices were determined, and their correlation with discharge parameters, matrix effects, the first ionization energies and sample shapes were investigated. It was found that discharge gas flow exerted a minor influence on RSF values in a nickel (Ni) metal sample, whereas discharge current significantly affected RSF, with variations up to 57.00 % for cobalt (59Co). The results revealed that matrix effects were more pronounced in metal oxides, with the relative standard deviation (RSD) of RSF for typical elements ranging from 25.17 % to 101.04 %. RSF values for the same element across different metal oxides showed a correlation with lattice binding energy (U0). Particularly, RSF values for 12 elements including 23Na, 27Al, 28Si, 45Sc, 52Cr, 56Fe, 59Co, 88Sr, 130Te, 138Ba, 139La and 140Ce within 7 metal oxides showed a significant correlation with U0 of the metal oxides. In terms of sample shape, pin samples generally yielded higher RSF values than flat samples in both metals and oxides. RSF accuracy was confirmed with standard samples of zirconium (Zr 73 MR10002 and Zr IARM 705–18) and iron oxides (Fe2O3-1 and Fe2O3-2) with relative errors within 17.50 % except for 12C. Subsequently, these RSF values were effectively utilized for the quantitative analysis of samples collected from the China Space Station (CSS). This comprehensive analysis elucidates the multifaceted influences on RSF values, enhancing the precision of trace element quantification in GD-MS.

Mechanistic Implications of the Varying Susceptibility of PAHs to Pyro-Catalytic Treatment as a Function of Their Ionization Potential and Hydrophobicity.

Transition metal catalysts in soil constituents (e.g., clays) can significantly decrease the pyrolytic treatment temperature and energy requirements for efficient removal of polycyclic aromatic hydrocarbons (PAHs) and, thus, lead to more sustainable remediation of contaminated soils. However, the catalytic mechanism and its rate-limiting steps are not fully understood. Here, we show that PAHs with lower ionization potential (IP) are more easily removed by pyro-catalytic treatment when deposited onto Fe-enriched bentonite (1.8% wt. ion-exchanged content). We used four PAHs with decreasing IP: naphthalene > pyrene > benz(a)anthracene > benzo(g,h,i)perylene. Density functional theory (DFT) calculations showed that lower IP results in stronger PAH adsorption to Fe(III) sites and easier transfer of π-bond electrons from the aromatic ring to Fe(III) at the onset of pyrolysis. We postulate that the formation of aromatic radicals via this direct electron transfer (DET) mechanism is the initiation step of a cascade of aromatic polymerization reactions that eventually convert PAHs to a non-toxic and fertility-preserving char, as we demonstrated earlier. However, IP is inversely correlated with PAH hydrophobicity (log Kow), which may limit access to the Fe(III) catalytic sites (and thus DET) if it increases PAH sorption to soil OM. Thus, ensuring adequate contact between sorbed PAHs and the catalytic reaction centers represents an engineering challenge to achieve faster remediation with a lower carbon footprint via pyro-catalytic treatment.

Correlation of Electron Configuration, Electronegativity, and Ionization Energy of Strontium on the Modification of Eutectic Si in High-Pressure Die Cast A380 Al–Si Alloys

Correlation of Electron Configuration, Electronegativity, and Ionization Energy of Strontium on the Modification of Eutectic Si in High-Pressure Die Cast A380 Al–Si Alloys

Synchrotron-based x-ray diffraction analysis of energetic ion-induced strain in GaAs and 4H-SiC

Strain engineering using ion beams is a current topic of research interest in semiconductor materials. Synchrotron-based high-resolution x-ray diffraction has been utilized for strain-depth analysis in GaAs irradiated with 300 keV Ar and 4H-SiC and GaAs irradiated with 100 MeV Ag ions. The direct displacement-related defect formation, anticipated from the elastic energy loss of Ar ions, can well explain the irradiation-induced strain depth profiles. The maximum strain in GaAs is evaluated to be 0.88% after Ar irradiation. The unique energy loss depth profile of 100 MeV Ag (swift heavy ions; SHIs) and resistance of pristine 4H-SiC and GaAs to form amorphous/highly disordered ion tracks by ionization energy loss of monatomic ions allow us to examine strain buildup due to the concentrated displacement damage by the elastic energy loss near the end of ion range (∼12 μm). Interestingly, for the case of SHIs, the strain-depth evolution requires consideration of recovery by ionization energy loss component in addition to the elastic displacement damage. For GaAs, strain builds up throughout the ion range, and the maximum strain increases and then saturates at 0.37% above an ion fluence of 3×1013 Ag/cm2. For 4H-SiC, the maximum strain reaches 4.6% and then starts to recover for fluences above 1×1013 Ag/cm2. Finally, the contribution of irradiation defects and the purely mechanical contribution to the total strain have been considered to understand the response of different compounds to ion irradiation.

Effects of Planarization of the Triphenylamine Unit on the Electronic and Transport Properties of Triarylamine-Fluorene Copolymers in Both Doped and Undoped Forms.

Triarylamine-alt-fluorene (TAF) copolymers are widely used for hole injection and transport in organic electronics. Despite suggestions to planarize the triphenylamine moiety, little research has been conducted. Here, we report a comprehensive investigation of the effects of planarization on the electronic and transport properties of a model TAF polymer semiconductor core. We compared the conventional twisted-propeller N-4-methoxyphenyl-N,N-diphenylamine-4',4″-diyl (TA) unit and its planarized bridged analogue (bTA) where adjacent o,o'-positions are linked by 1,1-dimethylmethylene. We studied both polyelectrolyte and non-polyelectrolyte forms of this core in both doped and undoped states. We found that planarization leads to an unprecedented trap-free transport of holes, and a pronounced enhancement of their mobility in the undoped state though less so in the doped state. Planarization also induces a slight reduction in the ionization energy of the undoped polymer, consequently lowering the work function of the doped polymer. This is accompanied by small spectral shifts: a red shift in the first absorption band of the undoped polymer and a blue shift in the first absorption band of the polaron. Furthermore, this study unveils new fundamental features of TAF polymers: (i) Doping induces the formation of three polaron bands within the subgap. (ii) Absorption of both neutral and polaron segments exhibit a linear intensity relationship with doping level. (iii) Electrical conductivity reaches a maximum at the half-doped state, varying as σ ∼ (x (1 - x))3 for 0.1 ≲ x ≲ 0.9, where x is the doping level. Finally, we demonstrate the successful integration of these self-compensated hole-doped TAF polymers as efficient hole injection layers in organic semiconductor diodes.

Nonlinear change of ion-induced secondary electron emission in the κ-Al2O3 surface charging from first-principle modelling

Secondary electron emission (SEE) induced by the positive ion is an essential physical process to influence the dynamics of gas discharge which relies on the specific surface material. Surface charging has a significant impact on the material properties, thereby affecting the SEE in the plasma-surface interactions. However, it does not attract enough attention in the previous studies. In this paper, SEE dependent on the charged surface of specific materials is described with the computational method combining a density functional theory (DFT) model from the first-principle theory and the theory of Auger neutralization. The effect of κ-Al2O3 surface charge, as an example, on the ion-induced secondary electron emission coefficient (SEEC) is investigated by analyzing the defect energy level and band structure on the charged surface. Simulation results indicate that, with the surface charge from negative to positive, the SEEC of a part of low ionization energy ions (such as E i = 12.6 eV) increases first and then decreases, exhibiting a nonlinear changing trend. This is quite different from the monotonic decreasing tendency observed in the previous model which simplifies the electronic structure. This irregular increase of the SEEC can be attributed to the lower escaped probability of orbital energy. The results further illustrate that the excessive charge could cause the bottom of the conduction band close to the valence band, thus leading to the decrease of the orbital energy occupied by the excited electrons. The nonlinear change of SEEC demonstrates a more realistic situation of how the electronic structure of material surface influences the SEE process. This work provides an accurate method of calculating SEEC from specific materials, which is urgent in widespread physical scenarios sensitive to surface materials, such as increasingly growing practical applications concerning plasma-surface interactions.

Robust structural superlubricity under gigapascal pressures

Structural superlubricity (SSL) is a state of contact with no wear and ultralow friction. SSL has been characterized at contact with van der Waals (vdW) layered materials, while its stability under extreme loading conditions has not been assessed. By designing both self-mated and non-self-mated vdW contacts with materials chosen for their high strengths, we report outstanding robustness of SSL under very high pressures in experiments. The incommensurate self-mated vdW contact between graphite interfaces can maintain the state of SSL under a pressure no lower than 9.45 GPa, and the non-self-mated vdW contact between a tungsten tip and graphite substrate remains stable up to 3.74 GPa. Beyond this critical pressure, wear is activated, signaling the breakdown of vdW contacts and SSL. This unexpectedly strong pressure-resistance and wear-free feature of SSL breaks down the picture of progressive wear. Atomistic simulations show that lattice destruction at the vdW contact by pressure-assisted bonding triggers wear through shear-induced tearing of the single-atomic layers. The correlation between the breakdown pressure and material properties shows that the bulk modulus and the first ionization energy are the most relevant factors, indicating the combined structural and electronic effects. Impressively, the breakdown pressures defined by the SSL interface could even exceed the strength of materials in contact, demonstrating the robustness of SSL. These findings offer a fundamental understanding of wear at the vdW contacts and guide the design of SSL-enabled applications.

Screened optimally tuned range separated hybrid functional for solvated low bandgap molecular systems.

The description of electronic properties of low bandgap molecular system is often performed by using density functional theory (DFT) and time dependent (TD) DFT calculations with the optimally tuned range-separated hybrid (OT-RSH) functional, as it contains the necessary ingredients to reliably predict charge transfer excitations. However, the range separating parameter (ω) is system-dependent and its optimization, including the chemical environment, is intricate. Refaely-Abramson et al. demonstrated that the gap renormalization in molecular crystals, a ground state property, can be represented by an OT-RSH functional screened by ɛstatic [Phys. Rev. B 88, 081204(R) (2013)], the zero frequency scalar dielectric constant. In this study, we propose the use of an OT-RSH functional screened by the scalar dielectric constant in the high frequency limit (OT-sRSH), ɛ∞, an appropriate constraint for vertical ionization energies or excitations in a dielectric environment. We have performed calculations for S,N-heteroacene derivatives in tetrahydrofuran and dichloromethane. The "unscreened" OT-RSH functional tends to underestimate experimental ionization potentials (IPs) and optical gaps (Egs) by up to 1.5 and 0.5eV, respectively. In contrast, OT-sRSH functional calculations underestimate IPs and Egs by only 0.4 and 0.2eV. We also compared the OT-sRSH results to explicitly solvated OT-RSH functional calculations for oligothiophenes in dioxane, benzene in ammonia, and methylene blue in water. We observe that both the approaches perform similarly for weakly interacting intermolecular systems and deviate for solvent-solute interacting systems, as expected. In conclusion, the OT-sRSH functional can describe molecular systems with environmental polarization effects accurately, a step toward describing realistic molecular systems.

Relativistic calculations for total energies, ionization energies, and one-electron binding energies for Neodymium ions Nd I to Nd[formula omitted]

We present the results of calculations for the total energies, ionization energies, and one-electron binding energies for ground-state configurations of neodymium ions Nd I to Nd59+. These calculations are based on the Dirac–Fock approximation taking the Breit and quantum electrodynamics corrections into account. The configuration interaction method, taking into account all relativistic configurations corresponding to the non-relativistic one, is used to obtain total energies and wave functions in the intermediate coupling scheme. Comparison is given with other available data.

Fermi energy modulation by tellurium doping of thermoelectric copper(I) iodide

Copper(I) iodide (CuI) is the leading inorganic p-type transparent conductor, attracting major attention for its promising optoelectronic properties and facile growth methods, although, commercial uptake is limited due to its as-of-yet insufficient electrical conductivity. Doping CuI with the chalcogens (O, S, Se, Te) is a viable route to tune its electrical conductivity for applications such as in thin film transistors, hole transport layers in solar cells, and transparent thermoelectric generators. The heaviest chalcogen element, Te, is yet to be explored in heavily intrinsically p-type doped CuI at non-alloying concentrations, the subject of the present work. We report the effects of tellurium at the boundary between the doping and alloying regime (up to a maximum of 2.4 % Te) in CuI thin films and investigation the variation in the thermoelectric properties and electronic band structure of the material. Ion implanting tellurium into CuI led to a progressive reduction in the films' work functions from 4.9 eV to 4.5 eV while the ionization potential remained unchanged, measured through photoemission spectrometry. This signified a modulation of the Fermi energy relative to the valence band edge, having a major effect on the materials' electrical conductivity and Seebeck coefficient, the former decreasing by 3 orders of magnitude, while the latter increased by 80 %. We conducted density functional theory (DFT) calculations to elucidate the effect of tellurium doping on the band structure of CuI. Tellurium doping corroborated the shift of Fermi energy, the incorporation of impurity acceptor states deeper into the band gap, in addition to disordering the valence band maximum. This work shows that, the Fermi energy in heavily p-type doped CuI can be moved away from the valence band through Te doping in addition to introducing band disorder, useful for controlling the hosts’ transport properties.

Selective adsorption of high ionization potential value organic pollutants in wastewater

It is imperative to devise effective removal strategies for high ionization potential (IP) organic pollutants in wastewater as their reduced electron-donating capacity challenges the efficiency of advanced oxidation systems in degradation. Against this backdrop, leveraging the metal-based carbon material structure meticulously, we employed metal-pyridine-N (M-N-C, M=Fe, Co, and Ni) as the electron transfer bridge. This distinctive design facilitated the ordered transfer of electrons from the adsorbent surface to the surface of high IP value pollutants, acting as a "supplement" to compensate for their deficient electron-donating capability, thereby culminating in the selective adsorption of these pollutants. Furthermore, this adsorbent also demonstrated effective removal of trace emerging contaminants (2 mg/L), displayed robust resistance to various salts, exhibited reusability, and maintained stability. These findings carry substantial implications for future carbon-based material design, offering a pathway toward exceptional adsorption performance in treating water pollution.