Electronic Topology Research Articles

Electronic structures and spin topologies of gamma-picoliniumyl radicals. A study of the homolysis of N-methyl-gamma-picolinium and of benzo-, dibenzo-, and naphthoannulated analogs.

Radicals resulting from one-electron reduction of (N-methylpyridinium-4-yl) methyl esters have been reported to yield (N-methylpyridinium-4-yl) methyl radical, or N-methyl-gamma-picoliniumyl for short, by heterolytic cleavage of carboxylate. This new reaction could provide the foundation for a new structural class of bioreductively activated, hypoxia-selective antitumor agents. N-methyl-gamma-picoliniumyl radicals are likely to damage DNA by way of H-abstraction and it is of paramount significance to assess their H-abstraction capabilities. In this context, the benzylic C-H homolyses were studied of toluene (T), gamma-picoline (P, 4-methylpyridine), and N-methyl-gamma-picolinium (1c, 1,4-dimethylpyridinium). With a view to providing capacity for DNA intercalation the properties also were examined of the annulated derivatives 2c (1,4-dimethylquinolinium), 3c (9,10-dimethylacridinium), and 4c (1,4-dimethylbenzo[g]quinolinium). The benzylic C-H homolyses were studied with density functional theory (DFT), perturbation theory (up to MP4SDTQ), and configuration interaction methods (QCISD(T), CCSD(T)). Although there are many similarities between the results obtained here with DFT and CI theory, a number of significant differences occur and these are shown to be caused by methodological differences in the spin density distributions of the radicals. The quality of the wave functions is established by demonstration of internal consistencies and with reference to a number of observable quantities. The analysis of spin polarization emphasizes the need for a clear distinction between "electron delocalization" and "spin delocalization" in annulated radicals. Aside from their relevance for the rational design of new antitumor drugs, the conceptional insights presented here also will inform the understanding of ferromagnetic materials, of spin-based signaling processes, and of spin topologies in metalloenzymes.

Theoretical study of structures and properties of cyclobutadiene, cyclopentadiene and benzene and their nitrogen isoelectronic equivalents

B3LYP/aug-cc-pvDZ level of theory is applied to study the geometric structures, electronic topologies, heats of formation, hyperconjugations and steric repulsions of 27 kinds of compounds obtained by successive replacement of CH groups with nitrogen atoms in cyclobutadiene, cyclopentadiene and benzene. The results reveal that the total energy linearly decreases along with the replacement of CH groups by nitrogen atoms for the three systems. To estimate the potential of high nitrogen content high energy materials (HNC–HEMs), heats of formation are calculated by G3 method. With the increase of the number of nitrogen atoms in ring, heats of formation increase substantially. The four-membered ring system is found to have the greatest heat of formations, followed by the six-membered ring system, and then by the five-membered ring system. Especially, hexazine and tetraazacyclobutadiene have great heats of formation relative to the other compounds, which implies that they should be applicable as HNC–HEMs. In addition, our studies indicate that the relationship between the total energy or heats of formation of isomers and the position of nitrogen atoms is (ortho) meta < (ortho) para < ortho. NBO analysis shows that it is hyperconjugation, not steric repulsion that plays a key role in the relative stability of isomers.

QSAR without arbitrary descriptors: the electron-conformational method

The electron-conformational (EC) method in QSAR problems employs a unique (based on first principles) descriptor of molecular properties that incorporates the electronic structure and topology of the molecule and is presented in a digital-matrix form suitable for computer processing, the EC matrix of congruity (ECMC). Its matrix elements have clear-cut physical meanings of interatomic distances, bond orders, and atomic reactivity (interaction indices). By comparing these matrices for several active compounds of the training set a group of matrix elements is revealed that are common for these compounds within a minimum tolerance, the EC submatrix of activity (ECSA). The latter is the numerical pharmacophore for the level of activity and diversity of the tried compounds. The EC method was described in detail and used for pharmacophore identification and quantitative bioactivity prediction elsewhere. In this paper we give further general considerations of its uniqueness and emphasize its advantages as compared with traditional QSAR methods, outlining the following three novel points: (1) The unique, non-arbitrary descriptor employed in the EC method avoids the shortcomings of the arbitrary chosen descriptors and statistical estimation of their weight in the evaluation of the pharmacophore used in traditional QSAR methods. Arbitrary descriptors may be interdependent ("non-orthogonal") and their sets are necessarily incomplete, hence they may lead to chance correlations and artifacts. The EC pharmacophore is void of these failures, thus deemed to be absolutely reliable within the accuracy of the experimental data and the diversity of the molecules used in its evaluation; (2) The tolerances in the matrix elements of the ECSA play a special role reflecting the flexibilities of the pharmacophore parameters and the dependence of the activity on the latter quantitatively; they are obtained in a minimization procedure; by increasing the tolerances one can get pharmacophores for larger intervals of activity. An advanced formula is derived for the activity as a function of the drug-receptor bonding energy which handles also the multi-conformational problem, and a regressional procedure is suggested to represent the interaction energy and the activity by the ECSA matrix elements or tolerances; (3) The possibility of bimolecular activity is discussed when a single molecule of the active compound has no pharmacophore, but the latter is present in the bimolecular structure. Examples are given from the problem of aquatic toxicity to fish.

Electronic structures, lattice dynamics, and electron–phonon coupling of simple cubic Ca under pressure

The electronic band structures, lattice dynamics and electron–phonon coupling (EPC) of simple cubic (sc) Ca under pressure have been investigated using first-principles calculations. Analysis of the calculated band structure and Fermi surface with pressure suggests that the predicted electronic topology transitions (ETT) at the X point is mainly responsible for the observed anomaly of the electrical resistance. The phonon calculations for sc Ca with both supercell and linear response methods reveal large imaginary frequencies in the pressure range of 32–109 GPa. This phonon instability might imply the existence of significant anharmonic effect in sc Ca needed to stabilize the crystal. In addition, EPC calculation demonstrates that the observed increase of the superconducting transition temperature T c with pressure is mainly attributed to the enhancement of the electron density of state at the Fermi level N ( E F ) and the EPC matrix element 〈 I 2 〉 .

An Ultrahigh-Speed, Low Power Electrical Drive System

New emerging applications in the areas of portable power generation, small turbocompressors and spindles require the development of ultrahigh-speed, low power electrical drives. A 500 000 r/min, 100 W electrical drive system is presented. Because of the ultrahigh-speed requirements, standard machine design and power electronic topology choices no longer apply and the complete drive system has to be considered. A permanent magnet machine with a slotless litz-wire winding is used, which results in a low motor inductance and a high fundamental machine frequency. Three different combinations of power electronic topologies and commutation strategies have been experimentally investigated. A voltage source inverter with block commutation and an additional dc-dc converter is selected as the most optimal choice for the power electronics interface as it results in the lowest volume of the entire drive system due to lower switching losses, no heat sink cooling required, a small number of semiconductor devices, and relatively simple control implementation in a low cost digital signal processor.

A probabilistic approach to optimizing power rating of interline power flow controllers in distributed generation power systems

High‐power electronic converter topologies, in such forms as Unified Power Flow Controllers (UPFC), Static Compensators (STATCOM) and Interline Power Flow Controllers (IPFC), have been used to enhance and optimize the use of transmission facilities, under the concept of a flexible ac transmission system (FACTS). In Europe, the anticipated proliferation of distributed‐generation (DG) in the near future, driven by governmental initiatives and the European Commission's Framework Programs, has prompted new interests in the reliability and economy of power delivery and interconnection at the lower sub‐station level of 15kV. This paper investigates the use of IPFC, which are dc/ac converters linked by common DC terminals, in a DG‐power system from an economy perspective. By using a probabilistic approach, it can be shown that the power ratings of parallel active power filters used in the IPFC are considerably reduced from those of the deterministic approach, when reliability is not compromised. Analytical predications, and experimental measurements at a 15kV substation fed by a number of wind generators, confirm the validity of the proposed approach.

Discovery of Singlet Diradicals: Theoretical Study on the Cage Species C14N12−H6 and Its Six Derivatives

In this work, the geometries, harmonic vibrational frequencies, and high-energy density material (HEDM) properties of a novel species and its six derivatives with the general formula C14N12-R6 (R = H, OH, F, CN, N3, NH2, and NO2) have been investigated at the restricted and unrestricted B3LYP/cc-pVDZ levels of theory. Natural bond orbital (NBO), natural orbital (NO), and atoms in molecules (AIM) analyses are applied to examine their electronic topologies. It is found that for the four species of R = H, CN, N3, and NO2, (1) there exist high LUMO occupation numbers, (2) there is considerable spin density congregated on the two central carbon atoms, (3) there exists through space interaction (or intramolecular interaction, which is one of the stabilizing factors of a diradicaloid) between the two central carbon atoms, (4) the distance (about 3 A) between the two central carbon atoms (as the apexes of two trigonal pyramids with their bases facing each other) is suitable and favorable for diradical formation. All the results support that these four species are diradicals or diradicaloids. Furthermore, the appreciable singlet-triplet energy gaps indicate that these four diradicals tend to have a singlet ground state. There is a moderate HOMO-LUMO gap (on the order of 1.5 to 2.1 eV) for these four species. These four singlet diradicals may be novel organic semiconductor materials or nonlinear optical materials. On the other hand, the remaining three species, with R = OH, F, and NH2, are not diradicaloids.

The Influence of the Startup Process of Small Metal-Halide (MH) Lamps on Electronic Ballast Design

In this paper, the authors present the results of an investigation into the starting process of a small wattage metal halide lamp and address the influence of the starting process, at extra- high frequency (>350 kHz), upon the performance of two most commonly used electronic ballast circuit topologies, namely the LCC resonant inverter and LCL resonant inverter. The starting transient processes driven by both ballast systems are captured, analyzed and explained. It has been found that the starting process could affect the operating performance of an LCL ballast and may destroy its power switches in the worst case while a LCC ballast gets the advantage over the LCL ballast for the stability during the transient starting process.

The metal-rich palladium chalcogenides Pd 2MCh2 ( M=Fe, Co, Ni; Ch=Se, Te): Crystal structure and topology of the electron density

Crystals of Pd 2 MCh 2 ( M=Fe, Co, Ni; Ch=Se, Te) were synthesized by heating the elements at 823–1323 K in silica ampoules under argon atmosphere. Their structures were determined by single-crystal X-ray diffraction at room temperature. The metallic compounds crystallize in a variant of the K 2ZnO 2 type ( Ibam, Z=4, Pd 2CoSe 2: a=5.993(1), b=10.493(2), c=5.003(1) Å; Pd 2FeSe 2: a=5.960(1), b=10.576(2), c=5.078(1) Å; Pd 2CoTe 2: a=6.305(1), b=11.100(2), c=5.234(1) Å; Pd 2NiTe 2: a=6.286(1), b=11.194(2), c=5.157(1) Å). One-dimensional ∞ 1 [ MC h 4 / 2 ] tetrahedra chains with remarkably short M— M bonds run along [001], separated by [Pd 2] dumbbells with palladium in fivefold coordination of selenium or tellurium atoms. The structure may also be described as a filled variant of the SiS 2 type. M atoms occupy 1 4 of the tetrahedral voids and the Pd atoms fill all octahedral voids in a distorted ccp motif of chalcogen atoms. Even though the Pd 2 MCh 2 compounds are isotypic to K 2ZnO 2 from the crystallographic viewpoint, we find a different bonding situation with additional homo- and heteronuclear metal–metal bonds between the Pd and Co atoms. The electronic structures and topologies of the electron densities of Pd 2CoSe 2 and isotypic Na 2CoSe 2 are analyzed and compared by using Bader's AIM theory. Different values of topological charge transfer and electron density flatness indices uncover striking quantitative differences in the nature of chemical bonding between the metallic compound Pd 2CoSe 2 and nonmetallic Na 2CoSe 2.

Three-Center−Two-Electron and Four-Center−Four-Electron Bonds. A Study by Electron Charge Density over the Structure of Methonium Cations

We study the electronic density charge topology of CH(5)(+) species 1 (C(s)()), 2 (C(s)()), and 3 (C(2)(v)) at ab initio level using the theory of atoms in molecules developed by Bader. Despite the reports of previous studies concerning carbocationic species, the methane molecule is protonated at the carbon atom, which clearly shows its pentacoordination. In addition to the fact that hydrogen atoms in the methonium molecule behave in a very fluxional fashion and that the energy difference among the species 1, 2, and 3 are very low, is important to point out that two different topological situations can be defined on the basis of our study of the topology of the electronic charge density. Then, the species 1 and 2 present a three-center-two-electron (3c-2e) bond of singular characteristics as compared with other carbocationic species, but in the species 3, the absence of a 3c-2e bond is noteworthy. This structure can be characterized through the three bond critical points found, corresponding to saddle points on the path bonds between the C-H(2,3,5) that lie in the same plane. These nuclei define a four-center interaction where the electronic delocalization produced among the sigma(C-H) bonds provide a stabilization of the three C-H bonds involved in this interaction (the remaining two C-H bonds are similar to those belonging to the nonprotonated species). Our results show that bonding situations with a higher number of atom arrays are possible in protonated hydrocarbons.

Chemical Bonding, Electron−Phonon Coupling, and Structural Transformations in High-Pressure Phases of Si

The nature of chemical bonding of the stable phases of Si at high pressure was analyzed. The effect of pressure is to promote sp electrons into the d orbitals, thus increasing the metallic character and reducing the dimensionality of covalent bonding. Localized covalent bonds, however, persist up to approximately 40 GPa (Si-VI, Cmca) and help to stabilize directional framework structures. At high pressures, Si becomes a metal, and the usual dense packed structures prevail. The existence of conducting and localized electrons gives rise to a combination of "steep and flat bands" near the Fermi level in Si-V. This peculiar electron topology in conjunction with low-frequency vibrations contributes to the relatively high superconducting temperature in Si-V and VI.

Local structure inLaMnO3andCaMnO3perovskites: A quantitative structural refinement of MnK-edge XANES data

Hole-doped perovskites such as ${\mathrm{La}}_{1\ensuremath{-}x}{\mathrm{Ca}}_{x}{\mathrm{MnO}}_{3}$ present special magnetic and magnetotransport properties, and it is commonly accepted that the local atomic structure around Mn ions plays a crucial role in determining these peculiar features. Therefore experimental techniques directly probing the local atomic structure, like x-ray absorption spectroscopy (XAS), have been widely exploited to deeply understand the physics of these compounds. Quantitative XAS analysis usually concerns the extended region [extended x-ray absorption fine structure (EXAFS)] of the absorption spectra. The near-edge region [x-ray absorption near-edge spectroscopy (XANES)] of XAS spectra can provide detailed complementary information on the electronic structure and local atomic topology around the absorber. However, the complexity of the XANES analysis usually prevents a quantitative understanding of the data. This work exploits the recently developed MXAN code to achieve a quantitative structural refinement of the Mn $K$-edge XANES of ${\mathrm{LaMnO}}_{3}$ and ${\mathrm{CaMnO}}_{3}$ compounds; they are the end compounds of the doped manganite series ${\mathrm{La}}_{x}{\mathrm{Ca}}_{1\ensuremath{-}x}{\mathrm{MnO}}_{3}$. The results derived from the EXAFS and XANES analyses are in good agreement, demonstrating that a quantitative picture of the local structure can be obtained from XANES in these crystalline compounds. Moreover, the quantitative XANES analysis provides topological information not directly achievable from EXAFS data analysis. This work demonstrates that combining the analysis of extended and near-edge regions of Mn $K$-edge XAS spectra could provide a complete and accurate description of Mn local atomic environment in these compounds.

A practical comparison among high-power-factor electronic ballasts with similar ideas

This paper provides a comparative analysis among four electronic ballast topologies with high power factor, employing the same switch for inverter and power factor correction stage. The analyses done are based on experimental results. A commercial electromagnetic ballast (EMB) is tested to provide a comparison with implemented electronic ballasts. The features of each topology are shown through the discussion of their advantages and disadvantages. The electronic ballasts are made for two 40-W fluorescent lamps at 50-kHz switching frequency and for a 110-V/sub rms/ 60-Hz utility line.

An Analysis Into the Dimming Control and Characteristic of Discharge Lamps

This paper provides some qualitative insights into, and a quantitative analysis of, the interrelationship between the ballast circuit parameters and the physical processes inside the lamp arc under dimming conditions. Qualitative explanation is supported by experimental observations on the dimming characteristics of fluorescent and high-intensity-discharge (HID) lamps. This understanding enables engineers to choose the right combination of dimming technique and electronic ballast topology for different types of discharge lamps. Verified by experiments, the fundamental approximation technique is used to characterize the frequency-control and voltage-control dimming technique for series-loaded and parallel-load resonant circuits.

Theoretical Study on the Bromomethane−Water 1:2 Complexes

Bromomethane-water 1:2 complexes have been theoretically studied to reveal the role of hydrogen bond and halogen bond in the formation of different aggregations. Four stable structures exist on the potential energy surface of the CH3Br(H2O)2 complex. The bromine atom acts mainly as proton acceptor in the four studied structures. It is also capable of participating in the formation of the halogen bond. The properties and characteristics of the hydrogen bond and the halogen bond are investigated employing several different quantum chemical analysis methods. Cooperative effects for the pure hydrogen bonds or the mixed hydrogen bonds with halogen bonds and the possibility of describing cooperative effects in terms of the topological analysis of the electronic density or the charge-transfer stabilization energy are discussed in detail. An atoms-in-molecules study of the hydrogen bond or the halogen bond in the bromomethane-water 1:2 complexes suggests that the electronic density topology of the hydrogen bond or the halogen bond is insensitive to the cooperative effect. The charge-transfer stabilization energy is proportional to the cooperative effect, which indicates the donor-acceptor electron density transfer to be mainly responsible for the trimer nonadditive effect.

A novel power inverter for switched reluctance motor drives

Although apparently simpler, the SRM drives are nowadays more expensive than their conventional AC drive counterparts. This is to a great extent caused by the lack of a standardised power electronic converter for SRM drives, which would be available on the market as a single module. A number of attempts were therefore made in recent times to develop novel power electronic converter structures for SRM drives, based on the utilization of a three-phase voltage source inverter (VSI), which is readily available as a single module. This paper follows this line of thought and presents a novel power electronic converter topology for SRM drives, which is entirely based on utilization of standard inverter legs. One of its most important feature is that both magnetizing and demagnetizing voltage may reach the DC-bus voltage level while being contemporarily applied during the conduction overlap in the SRM adjacent phases. At the same time, the voltage stress across the power switches equals the DC-bus voltage. The topology is functional in all operating regimes of the drive. Principle of operation is explained in detail for a three-phase SRM drive and experimental results obtained with a 6/4 switched reluctance motor, are included. Four inverter legs are required in this case. Some considerations, justifying the proposed converter topology from the point of view of the cost, are included.

A High Pressure Study on NH4Pb2Br5 Type Compounds Part II: Electronic Structure and Changes under High Pressure

AbstractIn this work, we present a theoretical study (based on DFT‐calculations) of the electronic properties of compounds crystallising in a NH4Pb2Br5 type structure in a wide pressure range. The main focus of this study is to elucidate the nature of bonding of the ns2‐cations at ambient and elevated pressure.For a better understanding of the structure and bonding, the DOS of these compounds are evaluated and discussed on the basis of a simple model assuming mainly ionic interactions. The calculations are complemented by an orbital analysis using the crystal orbital Hamilton population (COHP) and an analysis of the electronic density topology with the electron localisation function (ELF). Structural and theoretical investigations give results that are in excellent agreement: The DFT‐calculations confirm the existence of bonding interactions between the ns2‐cations at elevated pressure.Our study indicates that the “character” of the additional electron pair changes with increasing pressure from nonbonding to bonding in agreement with a simple model system of two interacting ns2‐cations.

Tri-s-triazine and Its Nitrogen Isoelectronic Equivalents: An ab Initio Study

To find the application of tri-s-triazine-based compounds, the geometric structures, electronic topologies, heats of formation, and relative specific impulses of tri-s-triazine and its nitrogen isoelectronic equivalents and decomposition of C3N10 have been studied by quantum chemical methods. The results reveal that all these species have a rigid planar structure and a conjugation system over the tricyclic ring, which is beneficial to their stabilities. The molecular electrostatic potential analysis for all the species shows that the central region of the ring has a very strong positive electrostatic potential, which suggests that these heterocyclic rings should be applicable as an anion recognition module in cyclophane chemistry. Along with the replacement of the CH groups by nitrogen atoms in the tri-s-triazine molecule, the heats of formation and relative specific impulses for the substituted products increase substantially. This result suggests the equivalent c is a good candidate for high-energy-density material.

Solid-State Circuit Breakers and Current Limiters for Medium-Voltage Systems Having Distributed Power Systems

State-of-the-art mechanical circuit breakers in medium-voltage systems allow a safe handling of short-circuits if the short circuit power of the grid is limited. Using delayed turn-off times, the circuit breakers can be coordinated with lower level protection gear. Hence, a high availability of the grid can be guaranteed. However, during a short-circuit a significant voltage sag can be noticed locally in the medium-voltage grid. Sensitive loads such as computers will fail even if the voltage returns within a few seconds. A semiconductor circuit breaker, however, is able to switch fast enough to keep voltage disturbance within acceptable limits. The optimization and selection of power electronic switch topologies is critical. In this paper, different semiconductors are briefly compared considering the requirements of a solid-state switch integrated into a 20-kV medium-voltage grid. Based on these semiconductor characteristics, various switch topologies are developed, which are compared under technical and economical aspects. It is shown that solid-state circuit breakers offer significant advantages when compared to present solutions and can be used in today's medium-voltage power systems.

Two-phase induction motor drives

This article starts with a presentation of the mathematical model for an asymmetrical two-phase induction motor drives (TPIM). This is followed by an analysis of TPIM behavior under variable frequency supply, with the running capacitor placed or removed from the circuit. This article attempts mainly to investigate the reasons for the lack of variable-speed drives. Consequently, the aptitude of the TPIMs for operating at variable speed is to be estimated and the suitable power electronic topologies identified. The most common form of a typical two-phase machine is the permanent split-capacitor motor (PSCM), usually recognized as the single-phase induction machine.