MO Method Research Articles

The Boron conundrum: the case of cationic clusters B n + with n = 2–20

We investigate the molecular and electronic structure and thermochemical properties of the cationic boron clusters B n + with n = 2–20, using both MO and DFT methods. Several functionals are used along with the MP2, G3, G3B3, G4, and CCSD(T)/CBS methods. The latter is the high accuracy reference. While the TPSS, TPSSh, PW91, PB86, and PBE functionals show results comparable to high-accuracy MO methods, both BLYP and B3LYP functionals are not accurate enough for three-dimensional (3D) structures. A negligible difference is observed between the B3LYP, MP2, and CCSD(T) geometries. A transition between 2D and 3D structures occurs for this series at the B16 +–B19 + sizes. While smaller clusters B n + with n ≤ 15 are planar or quasi-planar, a structural competition takes place in the intermediate sizes of B 16–19 + . The B20 + cation has a 3D tubular shape. The standard heats of formation are determined and used to evaluate the cluster stability. The average binding energy tends to increase with increasing size toward a limit. All closed-shell species B n + has an aromatic character, but an enhanced stability is found for B5 + and B13 + whose aromaticity and electron delocalization are analyzed using the LOL technique.

The Non-Isothermal Crystallization Kinetics of Dispersible Nano-SiO<sub>2</sub>/PA66 Composites

The PA66-based composites containing dispersible nano-SiO2 (DNS) were prepared in a twin-screw extruder by melt compounding. The microstructures of dispersible nano-SiO2/PA66 composites were investigated by means of TEM and XRD, and the non-isothermal crystallization behavior was studied through Jeziorny method and Mo method based on DSC analysis. The results showed that the dispersion of DNS was uniform in PA66 matrix, which could be related to surface structure of dispersible nano-SiO2. It was found from the study of the non-isothermal crystallization kinetics that dispersible nano-SiO2 possessed a heterogeneous nucleation capability in PA66 matrix, and its addition could hinder the motion of PA66 molecular chain, lower the crystallization temperature, and prolong the crystallization time of PA66. In addition, the activation energies for non-isothermal crystallization of neat PA66 and composites were also evaluated by the Kissinger method. The result showed that the activation energies of dispersible nano-SiO2/PA66 composites were higher than that of neat PA66.

Relationships Between Base-Catalyzed Hydrolysis Rates or Glutathione Reactivity for Acrylates and Methacrylates and Their NMR Spectra or Heat of Formation

The NMR chemical shift, i.e., the π-electron density of the double bond, of acrylates and methacrylates is related to the reactivity of their monomers. We investigated quantitative structure-property relationships (QSPRs) between the base-catalyzed hydrolysis rate constants (k1) or the rate constant with glutathione (GSH) (log kGSH) for acrylates and methacrylates and the 13C NMR chemical shifts of their α,β-unsaturated carbonyl groups (δCα and δCβ) or heat of formation (Hf) calculated by the semi-empirical MO method. Reported data for the independent variables were employed. A significant linear relationship between k1 and δCβ, but not δCα, was obtained for methacrylates (r2 = 0.93), but not for acrylates. Also, a significant relationship between k1 and Hf was obtained for both acrylates and methacrylates (r2 = 0.89). By contrast, log kGSH for acrylates and methacrylates was linearly related to their δCβ (r2 = 0.99), but not to Hf. These findings indicate that the 13C NMR chemical shifts and calculated Hf values for acrylates and methacrylates could be valuable for estimating the hydrolysis rate constants and GSH reactivity of these compounds. Also, these data for monomers may be an important tool for examining mechanisms of reactivity.

Investigations of the Non-Isothermal Crystallization Behavior of Polyamide 6/Polyethylene-Octene/Organomontmorillonite Nanocomposites

The crystallization behavior of polyamide 6/polyethylene-octene/organomontmoril- lonite (PA 6/POE/OMMT) nanocomposites fabricated via melting intercalation route was investigated using differential scanning calorimeter (DSC). The crystallization kinetics under non-isothermal conditions was analyzed by Jeziorny method and Mo method, and the crystallization kinetics parameters were obtained. It was found that nano-clay acted as a heterogeneous nucleation agent and the semi-crystallization time was prolonged with the OMMT loading increasing. The activation energy for non-isothermal crystallization of such nanocomposites was calculated according to the Huffman-Lauritzen theory. The average size of the composite nanocrystals was reduced with introduction of OMMT to the synthetic system.

Synthesis and Characterization via Molecular Quantum Parameters of 2H‐Thiazolo[3,2‐a]pyrimidine‐3,5,7(6H)‐trione

2H‐Thiazolo[3,2‐a]pyrimidine‐3,5,7(6H)‐trione (2) was synthesized and characterized via molecular quantum parameters using the PM3‐semiempirical MO method. This is considered the only route not previously reported in the literature to synthesize compound 2 from 2‐imino‐4‐thiazolidinone (1).

Crystallization kinetics and degradation of nanocomposites based on ternary blend of poly(L‐lactic acid), poly(methyl methacrylate), and poly(ethylene oxide) with two different organoclays

AbstractTernary polymer blends composed of poly(L‐lactic acid) (PLLA), poly(methyl methacrylate) (PMMA), and poly(ethylene oxide) (PEO) is used as matrix for nanocomposites with two clays: organically modified vermiculite (OVMT) and organically modified montmorillonite (Clo10A). The addition of PMMA in PLLA/PEO blend matrix reduces the chain mobility and retards the crystallization of PLLA/PEO. The retardation effect of PMMA on PLLA/PEO blend is less pronounced with higher PEO contents. The incorporation of OVMT and Clo10A is one common strategy to improve crystallization process as well as thermal and mechanical properties. The crystallization kinetics of polymer nanocomposites was found to be well described by the Mo method. The evolution of activation energy during nonisothermal course is analyzed using isoconversional method, and the trend of activation energy variation was found to be different for each of two organoclays. Thermal stability is improved by the incorporation of organoclays, where Clo10A induces better stability than that of OVMT. Enzymatic degradation tests showed that the nanocomposites with OVMT possessed higher stability on enzymatic attack and slower degradation. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

The influences of polyethylene glycol molecular weight on thermal stability, nonisothermal crystallization behavior, and morphology of poly(trimethylene terephthalate)/poly(ethylene oxide terephthalate) copolymers

A series of poly(trimethylene terephthalate)/poly(ethylene oxide terephthalate) copolymers with approximately 25 wt% PEG content were synthesized and investigated. The results showed that the thermal stability of copolymers increased with increasing Mn, PEG from 1000 to 4000 g/mol. However, the thermal stability of the copolymer with Mn, PEG = 300 g/mol was better than the copolymer with Mn, PEG = 600 g/mol. The nonisothermal crystallization kinetics of the copolymers was analyzed using Ozawa and Mo models, and only the Mo method was satisfactory in describing this system. Polarized optical microscopy revealed that all copolymers could form ring banded spherulites and the temperature window for their formation was basically identical for all copolymers. In addition, the spherulitic growth rate curves of copolymers exhibited a bell shape, and both the maximum growth rate and the crystallization temperature corresponding to the maximum growth rate increased with the increase in Mn, PEG.

Morphology, Structure, and Crystallization of LaCl Modified Hollow Glass Microspheres/ Poly(vinylidenefluoride) Composites

Poly(vinylidene fluoride)/hollow glass microspheres (PVDF/HGMs) composites were prepared by using lanthanum chloride surface modified HGMs. The morphology, structure, and crystallization of the PVDF/HGMs composites were investigated by scanning electron microscopy (SEM), X-ray diffraction (XRD), and differential scanning calorimetry (DSC), respectively. The results showed that the interaction between the HGMs and the PVDF was improved by lanthanum chloride modification. The crystal structure of the PVDF was not changed by the HGMs, but the crystallinity was decreased. In addition, the Jeziorny and the Mo methods were used to analyze the non-isothermal crystallization kinetics. The results showed that the HGMs decreased the crystallization rates and extended the crystallization time of the PVDF.

Thermorheology and Crystallization Behaviors of Polyethylenes: Effect of Molecular Attributes

Correlations between polyethylenes of different compositions and branching architectures and the temperature dependence of their viscoelastic behavior as well as the dependence of the nonisothermal crystallization behaviors on the cooling rate were described. To analyze the thermorheological behavior of the various classical polyethylenes, a method proposed by van Gurp and Palmen was utilized and the classical high-pressure low-density polyethylene (LDPE) was found to be thermorheologically complex, while for high-density polyethylene (HDPE) and linear low-density polyethylene (LLDPE), thermorheological simplicity was observed. The Avrami and Mo methods were applied to describe the nonisothermal crystallization kinetics of the different PEs for various cooling rate. The values of the kinetic parameter F(T), kinetic crystallization rate constant (Zc), and half-time of crystallization (t1/2) indicated that long-chain branching (LCB) had the role of being a heterogeneous nucleating agent and accelerated the ...

Effects of modified-process on the microstructure, internal bias field, and activation energy in CuO-doped NKN ceramics

Abstract In this study, (Na0.5K0.5)NbO3 + xCuO (NKNCx, where x = 0–1 mol%) were separately prepared using the two-step calcination process (BO method) and a conventional mixed oxide method (MO method). The microstructure of NKNCx ceramics prepared using the MO method exhibited obviously inhomogeneous microstructure. In contrast, the BO method improved the compositional homogeneity as well as the electrical properties. A high Qm value of 2100 was obtained for NKNCx ceramics prepared using the BO method. The ceramics prepared using the BO method exhibited the formation of more oxygen vacancies, resulting in an increase in the internal bias field. The value for the activation energy of the samples supports the presence of oxygen vacancies. The bulk density, dielectric loss, kp, Qm, d33 and ɛ33T/ɛ0 of the NKNCx ceramics prepared using the BO method were 4.488 g/cm3, 0.15%, 41.5%, 2100, 95 pC/N and 280, respectively.

Periodic calculations of excited state properties for solids using a semiempirical approach

The semiempirical SCF MO method MSINDO (modified symmetrically orthogonalized intermediate neglect of differential overlap) [T. Bredow and K. Jug, Electronic Encyclopedia of Computational Chemistry, 2004] is extended to the calculation of excited state properties through implementation of the configuration interaction singles (CIS) approach. MSINDO allows the calculation of periodic systems via the cyclic cluster model (CCM) [T. Bredow et al., J. Comput. Chem., 2001, 22, 89] which is a direct-space approach and therefore can be in principle combined with all molecular quantum-chemical techniques. The CIS equations are solved for a cluster with periodic boundary conditions using the Davidson-Liu iterative block diagonalization approach. As a proof-of-principle, MSINDO-CCM-CIS is applied for the calculation of optical spectra of ZnO and TiO(2), oxygen-defective rutile, and F-centers in NaCl. The calculated spectra are compared to available experimental and theoretical literature data. After re-adjustment of the empirical parameters the quantitative agreement with experiment is satisfactory. The present approximate approach is one of the first examples of a quantum-chemical methodology for solids where excited states are correctly described as n-electron state functions. After careful benchmark testing it will allow calculation of photophysical and photochemical processes relevant to materials science and catalysis.

19F NMR study on the complex of fluorinated vitamin D derivatives with vitamin D receptor: elucidation of the conformation of vitamin D ligands accommodated in the receptor.

Nuclear receptors mediate allosteric communications where ligand binding initiates a cascade of signal transduction. The interaction of vitamin D with vitamin D receptor (VDR) was investigated by (19)F NMR spectroscopy of the complexes of three fluorinated vitamin D derivatives with the full-length rat VDR-LBD. In the (19)F NMR spectra of the VDR-ligand complexes, the A-ring of 4,4-difluoro-1,25(OH)2D3 was revealed to adopt β-conformation in the VDR in solution, and the spectra were shown to be dependent on the dissociation constant. While the complex of 4,4-difluoro-1,25(OH)2D3 with VDR exhibited a clear distinguishable (19)F NMR spectrum, those of (19)F-1,25(OH)2D3 stereoisomers, which have 10-fold higher VDR affinity than 4,4-difluoro-1,25(OH)2D3, did not. The solid-phase NMR technique was useful for (19)F-1,25(OH)2D3 stereoisomers. The fluorinated vitamin D derivatives showed marked changes in the chemical shift (Δ4-19.7 ppm) upon VDR-complex formation, and the ab initio MO method suggested that van der Waals interactions play a major role in the complex formation.

Nonisothermal crystallization behavior, and morphology of poly(trimethylene terephthalate)/polyethylene glycol copolymers

Poly(trimethylene terephthalate)/polyethylene glycol (PTT/PEG) copolymers, with PEG content ranging from 27.2 to 47.4 wt%, were synthesized by melt copolycondensation. Wide-Angle X-ray diffractometer revealed that all copolymers had the same crystal structure of homo-PTT at room temperature. All copolymers could form ring-banded spherulites, and band spacing increased with increasing PEG content at a given crystallization temperature. Nonisothermal crystallization morphology of copolymers was greatly influenced by cooling rate. When the cooling rate was 2.5 °C/min or lower, banded patterns were absent, whereas when the cooling rate was 20 °C/min or higher, a novel crystal morphology composed of non-banded spherulites (central part) and ring-banded spherulites with decreasing band spacing along the radial growth direction was observed. Moreover, the size of the non-banded spherulitic part decreased with increasing cooling rate. Finally, the nonisothermal crystallization kinetics of copolymers were analyzed and only the Mo method was satisfactory to accurately describe this system.

Effects of improved process for CuO-Doped NKN lead-free ceramics on high-power piezoelectric transformers

In this paper, the effects of the electrical proper- ties of CuO-doped (Na(0.5)K(0.5))NbO(3) (NKN) ceramics prepared separately using the B-site oxide precursor method (BO method) and conventional mixed-oxide method (MO method) on high-power piezoelectric transformers (PTs) were investigated. The performances of PTs made with these two substrates were compared. Experimental results showed that the output power and temperature stability of PTs could be enhanced because of the lower resonant impedance of the ceramics prepared using the BO method. In addition, the output power of PTs was more affected by the resonant impedance than by the mechanical quality factor (Q(m)) of the ceramics. The PTs fabricated with ceramics prepared using the BO method showed a high efficiency of more than 94% and a maximum output power of 8.98 W (power density: 18.3 W/cm(3)) with temperature increase of 3°C under the optimum load resistance (5 kΩ) and an input voltage of 150 V(pp). This output power of the lead-free disk-type PTs is the best reported so far.

Solid-State Photocycloaddition Reactions between Di-2-Pyrones Tethered by Arylalkyl Chain and Benzophenones

Solid-state photocycloaddition reactions between di-2-pyrones (1a-d) with benzophenone (2a) gave the corresponding oxetane derivatives (3a-d; 1:2 adducts) with high site- and regioselectivity across the C5-C6 and C5′-C6′ double bonds in 1 via the triplet excited state of 2a. The reactions were inferred by MO methods to be initiated by electrostatic interaction between the C6 position of 1a-d and the carbonyl oxygen of 2a at their ground states, and the solid-state interaction may be enhanced by electron density at carbonyl oxygen of the triplet 2a. The transition state (TS) analysis of the [2+2] cycloaddition reactions also suggested some triplet complex, and the high regioselectivity. The hydrogen-bonding interaction between 2a and 1a-d and the triplet reaction mechanism were also explained by the IR analyses and the quenching experiments, respectively.

Investigation of CuO‐Doped NKN Ceramics with High Mechanical Quality Factor Synthesized by a B‐Site Oxide Precursor Method

In this study, composition of (Na0.5K0.5)NbO3 + x mol% CuO ceramics (NKNCx, where x = 0–1 mol%) were separately prepared using the B‐site oxide precursor method (BO method) and the conventional mixed oxide method (MO method). The diffracted angles of the NKNCx ceramics decreased as the concentrations of CuO dopants increased, because Nb5+ ions were replaced by Cu2+ ions, leading to the formation of oxygen vacancies. The microstructures of NKNCx ceramics prepared using the BO method were more homogeneous microstructures than that of ceramics prepared using the MO method. The mechanical quality factor (Qm) and dielectric constant (ε33T/ε0) of NKNCx ceramics prepared using the BO method were therefore by 21% and 25% better, respectively. The activation energy and internal bias field were measured and calculated to confirm the presence of oxygen vacancies. A low activation energy corresponds to a high Qm value. NKN ceramics with 0.75 mol% CuO doping prepared using the BO method had an activation energy and internal bias field of 0.95 eV and 3.5 kV/cm, respectively, at x = 0.75 mol%. The bulk density, kp, Qm, ε33T/ε0, and dielectric loss of NKNCx ceramics with this composition were 4.488 g/cm3, 41.5%, 2100, 280, and 0.15%, respectively.

Nonisothermal crystallization behavior of biodegradable poly(butylene terephthalate‐co‐butylene adipate‐co‐ethylene terephthalate‐co‐ethylene adipate) copolyester

AbstractA series of biodegradable aliphatic‐aromatic copolyester, poly(butylene terephthalate‐co‐butylene adipate‐co‐ethylene terephthalate‐co‐ethylene adipate) (PBATE), were synthesized from terephthalic acid (PTA), adipic acid (AA), 1,4‐butanediol (BG) and ethylene glycol (EG) by direct esterification and polycondensation. The nonisothermal crystallization behavior of PBATE copolyesters was studied by the means of differential scanning calorimeter, and the nonisothermal crystallization kinetics were analyzed via the Avrami equation modified by Jeziorny, Ozawa analysis and Z.S. Mo method, respectively. The results show that the crystallization peak temperature of PBATE copolyesters shifted to lower temperature at higher cooling rate. The modified Avrami equation could describe the primary stage of nonisothermal crystallization of PBATE copolyesters. The value of the crystallization half‐time (t1/2) and the crystallization parameter (Zc) indicates that the crystallization rate of PBATE copolyesters with more PTA content was higher than that with less PTA at a given cooling rate. Ozawa analysis was not suitable to study the nonisothermal crystallization process of PBATE copolyesters, but Z.S. Mo method was successful in treatingthis process. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers

Preparation, melting, glass relaxation and nonisothermal crystallization kinetics of a novel dendritic nylon-11

A novel dendritic nylon-11, DPA-11, is prepared from the melting copolycondensation of 11-aminoundecanoic acid and the 2nd generation poly(propyleneimine) dendrimer as the dendritic unit, with its melting, glass-transition and nonisothermal crystallization behaviors highlighted. DPA-11 is characterized using FTIR, TGA, WXRD and DSC. The results show that PDA-11 has excellent thermal stability, at room temperature its δ′-form crystal is predominant, and the dual melting processes and glass transition occur during the heating. The subsequent crystallization kinetic analysis with JMA, Ozawa and Mo methods demonstrates the mechanisms and crystallizability changing with the relative crystallinity, α, especially, during the primary and secondary crystallization stages. Moreover, applying the Vyazovkin method yields the dependence of the effective activation energy on crystallinity, from which the crystallization mechanisms are discussed in detail. Then the equilibrium melting temperature is determined, being 200.9 °C. Furthermore, the spherulitic growth analysis with the extended Hoffman–Lauritzen method produces the Regime I/II transition temperature of 158° C.

The [2 + 2 + 2] mechanisms of trimerization of three ethynes and monosilaethylenes

The mechanisms of [2 + 2 + 2] reactions of three ethynes and monosilaethylenes to form benzene and 1,3,5-trisilacyclohexane were studied by ab initio MO methods. The reaction mechanisms were analyzed by configuration interaction/localized molecular orbital/CASSCF calculations. Although the [2 + 2 + 2] reaction of ethyne is typically “homologous” concerted, that of monosilaethylene is polarized (ionic-cyclic) one-step reaction. In addition, the aromaticity along the intrinsic reaction coordinate pathway was studied using the index of deviation from aromaticity. Although the transition state of trimerization of ethyne does not have an aromatic nature for the σ- and π-bonds formation system, the crossing point of the σ-bond formation and π-bond breaking shows an aromatic nature.

Mechanical Properties, Morphology, Thermal Performance, Crystallization Behavior, and Kinetics of PP/Microcrystal Cellulose Composites Compatibilized by Two Different Compatibilizers

Polypropylene (PP)/microcrystalline cellulose (MCC) composites and PP/MCC composites modified by maleic anhydride grafted PP (PP-g-MA) and methyl acrylic acid glycidyl ester grafted PP (PP-g-GMA) respectively were prepared in a twin-screw extruder. The mechanical properties, morphology, and thermal performance were investigated. The nonisothermal crystallization, melting behavior, and nonisothermal crystallization kinetics were investigated by DSC. The results indicated that the addition of MCC had led to the increase of the tensile strength, impact strength, and flexural strength of PP. PP-g-GMA modification was more conducive to the improvement in tensile strength, impact strength, and flexural strength. The three types of PP/MCC composites have higher thermal decomposition temperatures, Vicat softening temperatures, and dimensional stability. Nonisothermal crystallizations of PP/MCC composites were in accordance with tridimensional growth with heterogeneous nucleation. Meanwhile, MCC was acted as the nucleating agent in PP matrix, which increased the crystallization temperature. PP-g-GMA further increased the crystallization temperature while PP-g-MA weakened the heterogeneous nucleation effect of MCC. Avrami equation and Mo method give a satisfactory description of the crystallization kinetics process. The activation energy of crystallization, nucleation constant, and fold surface free energy of PP were markedly reduced in PP/MCC composites and its compatibilized composites. The value of F( T) systematically increased with increasing relative degree of crystallinity. The addition of microcrystalline cellulose has greatly reduced the spherulitic size of PP.