Roles of Heterojunction and Cu Vacancies in the Au@Cu2-xSe for the Enhancement of Electrochemical Nitrogen Reduction Performance.

The utilization of hydrogen (H2) as a fuel source is hindered by the limited infrastructure and storage requirements. In contrast, ammonia (NH3) offers a promising solution as a hydrogen carrier due to its high energy density, liquid storage capacity, low cost, and sustainable manufacturing. NH3 has garnered significant attention as a key component in the development of next-generation refueling stations, aligning with the goal of a carbon-free economy. The electrochemical nitrogen reduction reaction (ENRR) enables the production of NH3 from nitrogen (N2) under ambient conditions. However, the low efficiency of the ENRR is limited by challenges such as the electron-stealing hydrogen evolution reaction (HER) and the breaking of the stable N2 triple bond. To address these limitations and enhance ENRR performance, we prepared Au@Cu2-xSe electrocatalysts with a core@shell structure using a seed-mediated growth method and a facile hot-injection method. The catalytic activity was evaluated using both an aqueous electrolyte of KOH solution and a nonaqueous electrolyte consisting of tetrahydrofuran (THF) solvent with lithium perchlorate and ethanol as proton donors. ENRR in both aqueous and nonaqueous electrolytes was facilitated by the synergistic interaction between Au and Cu2-xSe (copper selenide), forming an Ohmic junction between the metal and p-type semiconductor that effectively suppressed the HER. Furthermore, in nonaqueous conditions, the Cu vacancies in the Cu2-xSe layer of Au@Cu2-xSe promoted the formation of lithium nitride (Li3N), leading to improved NH3 production. The synergistic effect of Ohmic junctions and Cu vacancies in Au@Cu2-xSe led to significantly higher ammonia yield and faradaic efficiency (FE) in nonaqueous systems compared to those in aqueous conditions. The maximum NH3 yields were approximately 1.10 and 3.64 µg h-1 cm-2, with the corresponding FE of 2.24 and 67.52% for aqueous and nonaqueous electrolytes, respectively. This study demonstrates an attractive strategy for designing catalysts with increased ENRR activity by effectively engineering vacancies and heterojunctions in Cu-based electrocatalysts in both aqueous and nonaqueous media.

Manipulating wettability of catalytic surface for improving ammonia production from electrochemical nitrogen reduction.

An electrochemical nitrogen reduction reaction (ENRR) is considered a promising alternative for the traditional Haber-Bosch process. In this study, we present a method for improving the ENRR by controlling the wettability of the catalyst surface, suppressing the hydrogen evolution reaction (HER) while facilitating N2 adsorption. Reduced-graphene oxide (rGO) with a hydrophobic surface property and a contact angle (C.A.) of 59° was synthesized through a high-density atmospheric plasma deposition. Two other hydrophilic and superhydrophobic surfaces with a C.A. of 15° and 150° were developed through additional argon plasma and heat treatment of as-deposited rGO, respectively. The ENRR results showed that the ammonia yield and Faradaic efficiency tended to increase with increasing hydrophobicity. Electrochemical measurements reveal that superhydrophobic rGO achieves a higher Faradaic efficiency (5.73 %) at -0.1 V (vs RHE) and a higher NH3 yield (9.77 µg h-1 cm-2) at -0.4 V (vs RHE) in a 0.1 M KOH electrolyte. In addition, the computational fluid dynamics simulation confirmed that the amount of time the N2 gas remains on the surface could increase by improving the hydrophobicity of the catalytic surface. This study inspires the development of the rGO electrocatalyst through surface wettability modification for boosting ammonia electrosynthesis.

Synergistic Interaction of MoS2 Nanoflakes on La2Zr2O7 Nanofibers for Improving Photoelectrochemical Nitrogen Reduction.

Ammonia is a suitable hydrogen carrier with each molecule accounting for up to 17.65% of hydrogen by mass. Among various potential ammonia production methods, we adopt the photoelectrochemical (PEC) technique, which uses solar energy as well as electricity to efficiently synthesize ammonia under ambient conditions. In this article, we report MoS2@La2Zr2O7 heterostructures designed by incorporating two-dimensional (2D)-MoS2 nanoflakes on La2Zr2O7 nanofibers (MoS2@LZO) as photoelectrocatalysts. The MoS2@LZO heterostructures are synthesized by a facile hydrothermal route with electrospun La2Zr2O7 nanofibers and Mo precursors. The MoS2@LZO heterostructures work synergistically to amend the drawbacks of the individual MoS2 electrocatalysts. In addition, the harmonious activity of the mixed phase of pyrochlore/defect fluorite-structured La2Zr2O7 nanofibers generates an interface that aids in increased electrocatalytic activity by enriching oxygen vacancies in the system. The MoS2@LZO electrocatalyst exhibits an enhanced Faradaic efficiency and ammonia yield of approximately 2.25% and 10.4 µg h-1 cm-2, respectively, compared to their corresponding pristine samples. Therefore, the mechanism of improving the PEC ammonia production performance by coupling oxygen-vacant sites to the 2D-semiconductor-based electrocatalysts has been achieved. This work provides a facile strategy to improve the activity of PEC catalysts by designing an efficient heterostructure interface for PEC applications.

In Situ Grown CoMn2 O4 3D-Tetragons on Carbon Cloth: Flexible Electrodes for Efficient Rechargeable Zinc-Air Battery Powered Water Splitting Systems.

The integration of energy conversion and storage systems such as electrochemical water splitting (EWS) and rechargeable zinc-air battery (ZAB) is on the vision to provide a sustainable future with green energy resources. Herein, a unique strategy for decorating 3D tetragonal CoMn2 O4 on carbon cloth (CMO-U@CC) via a facile one-pot in situ hydrothermal process, is reported. The highly exposed morphology of 3D tetragons enhances the electrocatalytic activity of CMO-U@CC. This is the first demonstration of such a bifunctional activity of CMO-U@CC in an EWS system; it achieves a nominal cell voltage of 1.610 V @ 10 mA cm-2 . Similarly, the fabricated rechargeable ZAB delivers a specific capacity of 641.6 mAh gzn -1 , a power density of 135 mW cm-2 , and excellent cyclic stability (50 h @ 10 mA cm-2 ). Additionally, a series of flexible solid-state ZABs are fabricated and employed to power the assembled CMO-U@CC-based water electrolyzer. To the best of the authors' knowledge, this is the first demonstration of an in situ-grown binder-free CMO-U@CC as a flexible multifunctional electrocatalyst for a built-in integrated rechargeable ZAB-powered EWS system.

Size-Controlled Au-Cu2Se Core-Shell Nanoparticles and Their Thermoelectric Properties.

One promising approach to improving thermoelectric energy conversion is to use nanostructured interfaces that enhance Seebeck coefficient while reducing thermal conductivity. Here, we synthesized Au-Cu2Se core-shell nanoparticles with different shell thicknesses by controlling the precursor concentration in solution. The Au-Cu2Se core-shell nanoparticles are about 37-53 nm in size, and the cores of the nanostructures are composed of Au nanoparticles with sizes of ∼11 nm. The effect of shell thickness on the thermoelectric properties of core-shell nanocomposites is investigated after sintering the core-shell nanoparticles into pellets using the spark plasma sintering (SPS) technique. The power factor was optimized by the synergetic effect of the improvement of Seebeck coefficient by energy filtering in the Au/Cu2Se interface and the effective tuning of carrier concentration by Ohmic contact in the interface. The lattice thermal conductivity of core-shell nanocomposites is reduced by coherent phonon scattering, which is caused by the wavelike interference of phonons due to the phase shift in the core-shell interface. The highest ZT value of 0.61 is obtained at 723 K for Au-Cu2Se core-shell nanocomposite with a shell thickness of 21 nm, which is higher than that of pure Cu2Se nanocomposite or a mixture of Au and Cu2Se particles.

Gigantic Phonon-Scattering Cross Section To Enhance Thermoelectric Performance in Bulk Crystals.

In thermoelectric energy conversions, thermal conductivity reduction is essential for enhancing thermoelectric performance while maintaining a high power factor. Herein, we propose an approach based on coated-grain structures to effectively reduce the thermal conductivity to a much greater degree when compared to that done by conventional nanodot nanocomposite. By incorporating CdTe coated layers on the surface of SnTe grains, the thermal conductivity is as low as 1.16 W/m-K at 929 K, resulting in a thermoelectric figure of merit, i.e., zT, of 1.90. According to our developed theory, phonons scatter coherently due to the phase lag between phonons passing through and around the coated grain. Such scattering is induced by the acoustic impedance mismatch between the coated layer and the grain, resulting in a gigantic phonon-scattering cross section. The phonon-scattering cross section of the coated grains is several orders of magnitude larger than that of the nanodots with the same impurity concentration. The power factor was also slightly increased by the energy filtering effect at the coated surface and additional minority carrier blocking by the heterointerfaces. This scheme can be utilized for various bulk crystals, meaning a broad range of materials can be considered for thermoelectric applications.

Association between Cigarette Smoking Frequency and Health Factors among Korean Adults.

BACKGROUND: Recently, there has been a trend that cigarette smoking rate in Asian and Africa adults has increased while the age group to start smoking has decreased gradually. This study aimed to investigate the relationships between lifetime smoking and hypertension, diabetes, obesity, waist measure, fasting blood pressure and food consumption, in order to look into health status depending on smoking status in Koreans. METHODS: Totally, 1075 men and 697 women with no disease participated in this study, in which one-way ANOVA was conducted by using SPSS version 18.0 for statistical process. The level of statistical significance was 0.05. RESULTS: As a result of analysis on relationship between lifetime smoking and hypertension, obesity and diabetes, statistically significant differences were revealed.Lifetime smoking was found to be significantly associated with increased waist measure, higher level of fasting blood sugar, and more ingestion of nutrients (carbohydrate, fat, and protein). CONCLUSION: Increased amount of lifetime cigarette smoking was shown to negatively influence various health factors, which might become to be a drive to cause diseases. Therefore, method to improve health factors must be sought for via education and campaign to control an amount of cigarette smoking in Korean adults.

Thermoelectric Properties of Bi2Te3: CuI and the Effect of Its Doping with Pb Atoms.

In order to understand the effect of Pb-CuI co-doping on the thermoelectric performance of Bi2Te3, n-type Bi2Te3 co-doped with x at % CuI and 1/2x at % Pb (x = 0, 0.01, 0.03, 0.05, 0.07, and 0.10) were prepared via high temperature solid state reaction and consolidated using spark plasma sintering. Electron and thermal transport properties, i.e., electrical conductivity, carrier concentration, Hall mobility, Seebeck coefficient, and thermal conductivity, of CuI-Pb co-doped Bi2Te3 were measured in the temperature range from 300 K to 523 K, and compared to corresponding x% of CuI-doped Bi2Te3 and undoped Bi2Te3. The addition of a small amount of Pb significantly decreased the carrier concentration, which could be attributed to the holes from Pb atoms, thus the CuI-Pb co-doped samples show a lower electrical conductivity and a higher Seebeck coefficient when compared to CuI-doped samples with similar x values. The incorporation of Pb into CuI-doped Bi2Te3 rarely changed the power factor because of the trade-off relationship between the electrical conductivity and the Seebeck coefficient. The total thermal conductivity(κtot) of co-doped samples (κtot ~ 1.4 W/m∙K at 300 K) is slightly lower than that of 1% CuI-doped Bi2Te3 (κtot ~ 1.5 W/m∙K at 300 K) and undoped Bi2Te3 (κtot ~ 1.6 W/m∙K at 300 K) due to the alloy scattering. The 1% CuI-Pb co-doped Bi2Te3 sample shows the highest ZT value of 0.96 at 370 K. All data on electrical and thermal transport properties suggest that the thermoelectric properties of Bi2Te3 and its operating temperature can be controlled by co-doping.

A study on macronutrient self-selection after acute aerobic exercise in college females.

[Purpose] This study was conducted to determine whether acute aerobic exercise (climbing) is associated with changes in the dietary intake pattern. [Subjects and Methods] Food intake and physical activity data for 15 female college students were sampled for 3 days and categorized according to routine activity or high-intensity activity such as hiking. Nutrient intake based on the data was analyzed using a nutrition program. [Results] Carbohydrate and protein intake was significantly decreased after exercise compared to before acute aerobic exercise, but lipid intake showed no significant difference. Calorie intake was significantly decreased after exercise compared to before exercise; however, calorie consumption was significantly increased after exercise. [Conclusion] Aerobic exercise causes a decrease in total calories by inducing reduction in carbohydrate and protein intake. Therefore, aerobic exercise is very important for weight (body fat) control since it causes positive changes in the food intake pattern in female students.

Cationic Site-Preference in the Yb14-xCaxAlSb11 (4.81 ≤ x ≤ 10.57) Series: Theoretical and Experimental Studies.

Four quaternary Zintl phases with mixed-cations in the Yb14-xCaxAlSb11 (4.81 ≤ x ≤ 10.57) series have been synthesized by using the arc-melting and the Sn metal-flux reaction methods, and the isotypic crystal structures of the title compounds have been characterized by both powder and single-crystal X-ray diffraction (PXRD and SXRD) analyses. The overall crystal structure adopting the Ca14AlSb11-type can be described as a pack of four different types of the spiral-shaped one-dimensional octahedra chains with various turning radii, each of which is formed by the distorted ((Yb/Ca)Sb6) octahedra. Four symmetrically-independent cationic sites contain mixed occupations of Yb2+ and Ca2+ with different mixing ratios and display a particular site preference by two cationic elements. Two hypothetical structural models of Yb4Ca10AlSb11 with different cationic arrangements were designed and exploited to study the details of site and bond energies. QVAL values provided the rationale for the observed site preference based on the electronegativity of each atom. Density of states (DOS) curves indicated a semiconducting property of the title compounds, and crystal orbital Hamilton population (COHP) plots explained individual chemical bonding between components. Thermal conductivity measurement was performed for Yb8.42(4)Ca5.58AlSb11, and the result was compared to compounds without mixed cations.

Electromyography comparison of normal chair-desk system and assistant chair-desk system on fatigue.

[Purpose] This study was designed to test the effects of the Assistant Chair-Desk System (ACDS), which can reduce the forward tilt of the neck and trunk and the level of fatigue during long lasting study in the sitting position. [Subjects] Fourteen middle school students and 14 college students of mixed gender participated in this study. [Methods] Fatigue level, the trapezius muscle, and the forward tilt angle of the head and trunk as well as distance factors were assessed before after using a normal chair-desk system (NCDS) and the ACDS for 120 minutes. [Results] There was an interaction effect in the angle and length of the neck from the sitting posture changes after 2 hours of studying using the NCDS and ACDS. There were also significant differences in the fatigue levels, hip joint angles and the lengths from the head according to the main effects of the chair-systems. [Conclusion] The studying position while using the ACDS was determined to prevent significant fatigue levels of the muscle and body, provide support to the head, by limiting the forward movement of the neck, and prevent forward tilt of the neck and trunk, by enabling the target point and gaze to be closer to the horizontal direction.

Morphological Control of Bi2Te3 Nanotubes and Their Thermoelectric Properties.

Highly uniform Bi2Te3 nanotubes with various morphologies are synthesized via a solution process using Te nanowires as a sacrificial template. The morphology of Bi2Te3 nanotubes can be controlled by varying the solvent system. The reaction between Bi and Te in triethylene glycol (TEG) produces Bi2Te3 nanotubes with plate-like surface morphology, whereas rough surface morphology of the Bi2Te3 nanotubes is obtained by the reaction in ethylene glycol (EG). The crystal structures and morphologies of nanotubes are investigated X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM). The effect of solvent on the evolution of morphology of the Bi2Te3 nanotubes is investigated. The effect of surface morphology on the thermoelectric properties is discussed.

Effect of Nb on the Microstructure, Mechanical Properties, Corrosion Behavior, and Cytotoxicity of Ti-Nb Alloys.

In this paper, the effects of Nb addition (5-20 wt %) on the microstructure, mechanical properties, corrosion behavior, and cytotoxicity of Ti-Nb alloys were investigated with the aim of understanding the relationship between phase/microstructure and various properties of Ti-xNb alloys. Phase/microstructure was analyzed using X-ray diffraction (XRD), SEM, and TEM. The results indicated that the Ti-xNb alloys (x = 10, 15, and 20 wt %) were mainly composed of α + ß phases with precipitation of the isothermal ω phase. The volume percentage of the ω phase increased with increasing Nb content. We also investigated the effects of the alloying element Nb on the mechanical properties (including Vickers hardness and elastic modulus), oxidation protection ability, and corrosion behavior of Ti-xNb binary alloys. The mechanical properties and corrosion behavior of Ti-xNb alloys were found to be sensitive to Nb content. These experimental results indicated that the addition of Nb contributed to the hardening of cp-Ti and to the improvement of its oxidation resistance. Electrochemical experiments showed that the Ti-xNb alloys exhibited superior corrosion resistance to that of cp-Ti. The cytotoxicities of the Ti-xNb alloys were similar to that of pure titanium.

Cytotoxicity of soft denture lining materials depending on their component types.

PURPOSE: To evaluate the difference in cytotoxicity of soft denture lining materials depending on their component types. MATERIALS AND METHODS: Ten commercially available soft denture lining materials (SDLM) consisting of five silicone-based materials and five acrylic-based materials were evaluated. For the MTT test, cured SDLM samples were extracted in a culture medium for 24 hours, and L-929 cells were incubated in the extracted medium for 24 hours. Cell viability was determined using a microplate reader and compared with those of the negative control, which were cultured in a culture medium without test material. Agar overlay test was performed for the cured SDLM samples according to International Organization for Standardization (ISO) 7405. RESULTS: Among silicone-based lining materials, GC Reline Soft, Mollosil plus, and Dentusil showed a cell viability of 107.2% ± 4.5%, 102.3% ± 2.84%, and 93.0% ± 8.0%, respectively, compared with the control. Mucopren and Sofreliner Tough displayed significantly lower cell viability (86.4% ± 10.3% and 81.5% ± 4.3%,respectively) compared with the control (P < .05). Among acrylic-based materials, Kooliner, Visco-gel, Soft liner, Dura Base, and Coe-Soft displayed cell viability of 99.2% ± 14.6%, 93.1% ± 9.5%, 89.1% ± 9.8%, 87.6% ± 7.9%, and 75.9% ± 15.7%, respectively, compared with the control. Dura Base and Coe-Soft displayed significantly lower cell viability compared to the control. However, for all tested materials, cell viability exceeded the requirement limit of 70% specified in ISO 10993-5. In the agar overlay test, all five silicone-based materials and acrylic-based Kooliner were ranked as "noncytotoxic." However, Visco-gel was ranked as "mildly cytotoxic," and Soft liner, Coe-Soft, and Dura Base were ranked as "moderately cytotoxic." CONCLUSION: When an acrylic-based soft denture lining material is used, the possibility of a cytotoxic effect should be considered.

Massive Transformation in Titanium-Silver Alloys and Its Effect on Their Mechanical Properties and Corrosion Behavior.

In order to investigate the relationship between phase/microstructure and various properties of Ti-xAg alloys, a series of Ti-xAg alloys with Ag contents ranging from 5 to 20 wt% were prepared. The microstructures were characterized using X-ray diffractometry (XRD), optical microscopy (OM), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). All of the Ti-xAg alloys showed a massive transformation from the ß-Ti to αm phase, which has a different crystal structure from that of the matrix phase, but it has the same composition as the matrix α-Ti phase. As a result of solid-solution strengthening of α-Ti and massive transformation phase, the Ti-xAg showed better mechanical properties than the commercially pure titanium (cp-Ti). Electrochemical results showed that the Ti-xAg alloys exhibited improved corrosion resistance and oxidation resistance than cp-Ti.

Microstructure Analysis of Ti-xPt Alloys and the Effect of Pt Content on the Mechanical Properties and Corrosion Behavior of Ti Alloys.

The microstructure, mechanical properties, and corrosion behavior of binary Ti-xPt alloys containing 5, 10, 15 and 20 wt% Pt were investigated in order to develop new Ti-based dental materials possessing superior properties than those of commercially pure titanium (cp-Ti). All of the Ti-xPt (x = 5, 10, 15, 20) alloys showed hexagonal α-Ti structure with cubic Ti3Pt intermetallic phase. The mechanical properties and corrosion behavior of Ti-xPt alloys were sensitive to the Pt content. The addition of Pt contributed to hardening of cp-Ti and to improving its oxidation resistance. Electrochemical results showed that the Ti-xPt alloys exhibited superior corrosion resistance than that of cp-Ti.

n-Type nanostructured thermoelectric materials prepared from chemically synthesized ultrathin Bi2Te3 nanoplates.

We herein report on the large-scale synthesis of ultrathin Bi(2)Te(3) nanoplates and subsequent spark plasma sintering to fabricate n-type nanostructured bulk thermoelectric materials. Bi(2)Te(3) nanoplates were synthesized by the reaction between bismuth thiolate and tri-n-octylphosphine telluride in oleylamine. The thickness of the nanoplates was ~1 nm, which corresponds to a single layer in Bi(2)Te(3) crystals. Bi(2)Te(3) nanostructured bulk materials were prepared by sintering of surfactant-removed Bi(2)Te(3) nanoplates using spark plasma sintering. We found that the grain size and density were strongly dependent on the sintering temperature, and we investigated the effect of the sintering temperature on the thermoelectric properties of the Bi(2)Te(3) nanostructured bulk materials. The electrical conductivities increased with an increase in the sintering temperature, owing to the decreased interface density arising from the grain growth and densification. The Seebeck coefficients roughly decreased with an increase in the sintering temperature. Interestingly, the electron concentrations and mobilities strongly depended on the sintering temperature, suggesting the potential barrier scattering at interfaces and the doping effect of defects and organic residues. The thermal conductivities also increased with an increase in the sintering temperature because of grain growth and densification. The maximum thermoelectric figure-of-merit, ZT, is 0.62 at 400 K, which is one of the highest among the reported values of n-type nanostructured materials based on chemically synthesized nanoparticles. This increase in ZT shows the possibility of the preparation of highly efficient thermoelectric materials by chemical synthesis.

Exploring resonance levels and nanostructuring in the PbTe-CdTe system and enhancement of the thermoelectric figure of merit.

We explored the effect of Cd substitution on the thermoelectric properties of PbTe in an effort to test a theoretical hypothesis that Cd atoms on Pb sites of the rock salt lattice can increase the Seebeck coefficient via the formation of a resonance level in the density of states near the Fermi energy. We find that the solubility of Cd is less than previously reported, and CdTe precipitation occurs to create nanostructuring, which strongly suppresses the lattice thermal conductivity. We present detailed characterization including structural and spectroscopic data, transmission electron microscopy, and thermoelectric transport properties of samples of PbTe-x% CdTe-0.055% PbI(2) (x = 1, 3, 5, 7, 10), PbTe-1% CdTe-y% PbI(2) (y = 0.03, 0.045, 0.055, 0.08, 0.1, 0.2), PbTe-5% CdTe-y% PbI(2) (y = 0.01, 0.03, 0.055, 0.08), and PbTe-1% CdTe-z% Sb (z = 0.3, 0.5, 1, 1.5, 2, 3, 4, 5, 6). All samples follow the Pisarenko relationship, and no enhancement of the Seebeck coefficient was observed that could be attributed to a resonance level or a distortion in the density of states. A maximum ZT of approximately 1.2 at approximately 720 K was achieved for the PbTe-1% CdTe-0.055% PbI(2) sample arising from a high power factor of approximately 17 microW/(cm K(2)) and a very low lattice thermal conductivity of approximately 0.5 W/(m K) at approximately 720 K.

An application of the "coloring problem": structure-composition-bonding relationships in the magnetocaloric materials LaFe13-xSix.

The LaFe(13)-(x)Si(x) (1.0 < or = x < or = 5.0) series is studied experimentally and theoretically to gain possible understanding for the relationships among geometrical structure, chemical composition, magnetic behavior, and physical properties as related to the magnetocaloric effect in these compounds. As the Si concentration increases, LaFe(13)-(x)Si(x) exhibits a structural transformation from the cubic NaZn(13) structure type to a tetragonal derivative due primarily to preferential ordering of Fe and Si atoms. At room temperature, LaFe(13)-(x)Si(x) crystallize in the cubic structure for the range 1 < or = x < or = 2.6 and in the tetragonal for 3.2 < or = x < or = 5. In the range 2.6 < or = x < or = 3.2, it shows a two-phase mixture. Temperature-dependent single-crystal X-ray diffraction experiments near the corresponding Curie temperatures were performed on the room-temperature cubic phases to examine the origin of the large isothermal magnetic entropy changes. A thorough statistical and structural analysis of the data indicates that the noncentrosymmetric F43c space group provides a more adequate atomic arrangement than the centrosymmetric Fm3c space group. This change in space group leads to divergence for specific sets of Fe-Fe distances below the Curie temperature that arises from tilting of Fe-centered [Fe(12)-(x)Si(x)] icosahedra. The noncentrosymmetric space group also agrees with the predominance of icosahedral clusters lacking local inversion symmetry. From extended Hückel and tight-binding linear muffin-tin orbital (TB-LMTO) electronic structure calculations on various model structures, the F43c model is more energetically favorable than the Fm3c model. Extended Hückel calculations on various icosahedral [Fe(12)-(n)Si(n)] (n = 1-5) clusters and TB-LMTO calculations on "LaFe(13)," LaFe(11)Si(2), and LaFe(9)Si(4) have also been carried out to study the effects of a main group element (Si) on stabilizing the cubic NaZn(13)-type structure, influencing the transformation between cubic and tetragonal symmetries, and to study relationships among their chemical bonding and magnetic properties.