Electric‐field tuning of magnetoelectric properties in Metglas/piezofiber composites

The tunability of magnetoelectric (ME) properties by applied dc electric field (E) was systematically investigated for a laminate composite consisting of Metglas, Pb(Zr_x Ti_1–x)O₃ fiber, and interdigitated electrodes. The ME coefficients and equivalent magnetic noise were found to be dependent on E. This dependence is attributed to variations in the magnetic properties. The dielectric properties and noise charge density were relatively invariant to E. A 1.3× improvement in the ME coefficient was obtained at the Villari point under E = 300 V/mm relative to E = 0 V/mm. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

On the Plasma Chemistry of an RF Discharge Containing Aluminium Tri‐Isopropoxide Studied by FTIR Spectroscopy

In Ar and Ar/N₂ radio frequency (RF) discharges with admixtures of aluminium tri‐isopropoxide (ATI) the fragmentation of this metal‐organic precursor was studied by means of Fourier Transform Infrared (FTIR) spectroscopy using an optical long path cell providing an optical length of l = 17.2 m. The experiments were performed in an asymmetric capacitively coupled process plasma at a frequency of f = 13.56 MHz and at pres‐sure values in the range of p = 1–10.5 Pa. The discharge power was chosen between P = 10–100 W. Using FTIR spectroscopy the evolution of the concentrations of ATI and of six stable molecules, CH₄, C₂H₂, C₂H₄, C₂H₆, CO and HCN, was monitored under flowing conditions at gas flows of Φ_total = 0.5–14.5 sccm in the discharge. The concentrations of the reaction products were measured tobe between 2 x 10¹² molecules cm^–3 as e.g. found for C₂H₄and C₂H₆, and 5 x 10¹³ molecules cm^–3, as e.g. in the case of CO. In the plasma a complete dissociation of the precursor ATI was found at a power value of about P = 80 W independent on the admixture of Ar or N₂. The fragmentation efficiency (F_E) of the reaction products which originate from the ATI molecules ranges between 0.2 and 4 x 10¹⁶ molecules J^–1 while the fragmentation rate (F_R) reached up to 2.5 x 10¹⁸ molecules s^–1. The multi component detection ability of the spectrometer served to analyse the carbon balance of the by‐product formation. For all experiments, the carbon balance never exceeded 25%. Therefore, in the plasmas the majority of the provided carbon is most likely deposited at the reactor walls or forms dust particles or higher molecular C_xH_y. The conversion efficiencies (C_E) of the produced molecular species ranges between 0.1 x 10¹⁵ molecules J^–1 for C₂H₄ and 5 x 10¹⁵ molecules J^–1 for C₂H₆ depending on the discharge conditions of the RF plasma. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Measurement of wurtzite ZnO/rutile TiO2 heterojunction band offsets by x-ray photoelectron spectroscopy

Four novel dmit complexes: [(C₂H₅)₄N][Ni (dmit)₂], [(C₃H₇)₄N][Ni(dmit)₂], [(C₂H₅)₄N][Au(dmit)₂] and [(C₃H₇)₄N][Au(dmit)₂], abbreviated as EtNi, PrNi, EtAu, and PrAu, were synthesized. The third-order nonlinear optical properties of them in acetonitrile solutions were investigated by using the Z-scan technique with 20 ps pulses width at 1064 nm. When the on-axis irradiance at focus I ₀ was 5.025 GW/cm², the nonlinear refraction coefficient n ₂, the third-order nonlinear susceptibility χ ⁽³⁾, the molecular second-order hyperpolarizability γ of the four types of material were obtained with subject to Z-scan curves, and these indexes were with the magnitudes of 10⁻¹⁸ m²/W, 10⁻¹³ esu, and 10⁻³¹ esu, respectively. The nonlinear absorption coefficient β of Ni samples had the 10⁻¹² m/W scale. The impact of different metals and cations on the third-order nonlinear optical properties of materials was analyzed. Through the derivation, the result suggests that these dmit complexes are promising candidates for applications to nonlinear optical devices manufacture in the near-infrared waveband.     

Hartree–Fock and density functional theory study of remote substituent effects on heterolytic Fe–N bond energies of p‐G‐C6H4NHFe(CO)2(η5‐C5H5) and p‐G‐C6H4N(COMe)Fe(CO)2(η5‐C5H5)

The nature and strength of metal–ligand bonds in organotransition‐metal complexes are crucial to the understanding of organometallic reactions and catalysis. Quantum chemical calculations at different levels of theory have been used to investigate heterolytic Fe–N bond energies of para‐substituted anilinyldicarbonyl(η⁵‐cyclopentadienyl)iron [p‐G‐C₆H₄NH(η⁵‐C₅H₅)Fe(CO)₂, abbreviated as p‐G‐C₆H₄NHFp (1), where G = NO₂, CN, COMe, CO₂Me, CF₃, Br, Cl, F, H, Me, MeO, and NMe₂] and para‐substituted α‐acetylanilinyldicarbonyl(η⁵‐cyclopentadienyl)iron [p‐G‐C₆H₄N(COMe)(η⁵‐C₅H₅)Fe(CO)₂, abbreviated as p‐G‐C₆H₄N(COMe)Fp (2)] complexes. The results show that BP86 and TPSSTPSS can provide the best price/performance ratio and more accurate predictions in the study of ΔH_het(Fe–N)'s. The linear correlations [r = 0.98 (g, 1a), 0.93 (g, 2b)] between the substituent effects of heterolytic Fe–N bond energies [ΔΔH_het(Fe–N)'s] of series 1 and 2 and the differences of acidic dissociation constants (ΔpK_a) of N–H bonds of p‐G‐C₆H₄NH₂ and p‐G‐C₆H₄NH(COMe) imply that the governing structural factors for these bond scissions are similar. And the linear correlations [r = ?0.99 (g, 1c), ?0.92 (g, 2d)] between ΔΔH_het(Fe–N)'s and the substituent σ_p^? constants show that these correlations are in accordance with Hammett linear free energy relationships. The polar effects of these substituents and the basis set effects influence the accuracy of ΔH_het(Fe–N)'s. ΔΔH_het(Fe–N)'s(1, 2) follow the captodative principle. ME_{α‐COMe, para‐G}s include the influences of the whole molecules. The correlation of ME_{α‐COMe, para‐G}s with σ_p^? is excellent. ME_{α‐COMe, para‐G}s rather than ΔΔH_het(Fe–N)'s in series 2 are more suitable indexes for the overall substituent effects on ΔH_het(Fe–N)'s(2). Insight from this work may help the design of more effective catalytic processes. Copyright © 2012 John Wiley & Sons, Ltd.     

Solvatochromic properties of long alkyl chain π* indicators: comparison of N,N‐dialkyl‐4‐nitroanilines and alkyl 4‐nitrophenyl ethers

Hydrophobic forms of the N,N‐dialkyl‐4‐nitroaniline (DNAP) (p‐O₂NC₆H₄NR₂) ( 1a–f ) and alkyl‐4‐nitrophenyl ether (p‐O₂NC₆H₄OR) ( 2a–c ) solvatochromic π* indicators have been characterized and compared with respect to: (a) solvatochromic bandshape, (b) sensitivity expressed as ?s , ( / d π * ), and (c) trends in ? s with increasing length of alkyl chain(s) on the probe molecule. ? Octyl 4‐nitrophenyl ether (p‐O₂NC₆H₄OC₈H₁₇) ( 2b ) and ? decyl 4‐nitrophenyl ether (p‐O₂N C₆H₄ OC₁₀H₂₁) ( 2c ) were synthesized and their solvatochromic UV/Vis absorption bands were found to maintain a Gausso‐Lorentzian bandshape for the indicators in non‐polar and alkyl substituted aromatic solvents, for example, hexane(s) and mesitylene. Corresponding absorption bands for 1a–f display increasing deviation from a Gausso‐Lorentzian shape in the same solvents as the alkyl chains on the indicator are increased in length all the way to C₁₀ and C₁₂, for example, N,N‐didecyl‐4‐nitroaniline (p‐O₂NC₆H₄N (C₁₀H₂₁)₂) and N,N‐didodecyl‐4‐nitroaniline (p‐O₂NC₆H₄N (C₁₂H₂₅)₂) ( 1d–f ). A plot of ? s versus C_n follows a 1st order decay for the DNAP indicators but is linear for the alkyl 4‐nitrophenyl ethers. A discussion of how the long alkyl chains on the two types of indicators affect the orientation and overlap of n and π * orbitals, and resulting solvatochromic bands is presented. For DNAP, overextending the alkyl chains to obtain greater hydrophobic character may cause the alkane component to dominate solute‐solvation processes at the expense of the probe's fundamental solvatochromic character. Copyright © 2007 John Wiley & Sons, Ltd.     

Hartree–Fock and density functional theory study of remote substituent effects on gas‐phase heterolytic Fe–O and Fe–S bond energies of p‐G‐C6H4OFe(CO)2(η5‐C5H5) and p‐G‐C6H4SFe(CO)2(η5‐C5H5)

The knowledge of accurate bond strengths is a fundamental basis for a proper analysis of chemical reaction mechanisms. Quantum chemical calculations at different levels of theory have been used to investigate heterolytic Fe–O and Fe–S bond energies of para‐substituted phenoxydicarbonyl(η⁵‐cyclopentadienyl) iron [p‐G‐C₆H₄O(η⁵‐C₅H₅)Fe(CO)₂, abbreviated as p‐G‐C₆H₄OFp ( 1 ), where G = NO₂, CN, COMe, CO₂Me, CF₃, Br, Cl, F, H, Me, MeO, and NMe₂] and para‐substituted benzenethiolatodicarbonyl(η⁵‐cyclopentadienyl) iron [p‐G‐C₆H₄S(η⁵‐C₅H₅)Fe(CO)₂, abbreviated as p‐G‐C₆H₄SFp ( 2 )] complexes. The results show that BP86 and TPSSTPSS can provide the best price/performance ratio and more accurate predictions in the study of ΔH_het(Fe–O)'s and ΔH_het(Fe–S)'s. The excellent linear free‐energy relations [r = 0.99 (g, 1a), 1.00 (g, 2b)] among the ΔΔH_het (Fe–O)'s and Δpk_a's of O–H bonds of p‐G‐C₆H₄OH or ΔΔH_het(Fe‐S)'s and Δpk_a's of S–H bonds of p‐G‐C₆H₄SH imply that the governing structural factors for these bond scissions are similar. And the linear correlations [r = ?0.99 (g, 1g), ?0.98 (g, 2h)] among the ΔΔH_het (Fe‐O)'s or ΔΔH_het(Fe‐S)'s and the substituent σ_p^? constants show that these correlations are in accordance with Hammett linear free‐energy relationships. The polar effects of these substituents and the basis set effects influence the accuracy of ΔH_het(Fe–O)'s or ΔH_het(Fe–S)'s. ΔΔH_het(Fe–O)'s(g) ( 1 ) and ΔΔH_het(Fe–S)'s(g)( 2 ) follow the Capto‐dative principle. The substituent effects on the Fe–O bonds are much stronger than those on the less polar Fe–S bonds. Insight from this work may help the design of more effective catalytic processes. Copyright © 2013 John Wiley & Sons, Ltd.     

Experimental characterization of temperature‐dependent electron transport in single‐wall multi‐tube carbon nanotube transistors

Current–voltage, radio‐frequency (RF) and noise characteristics of single‐wall multi‐tube carbon nanotube (CNT) transistors were measured at cryogenic temperatures. Compared to an ambient temperature (T_a) of 300 K, only a slight drain current increase at T_a = 77 K was observed. In addition, a weak dependence of the maximum value of the current gain cut‐off frequency (f_T) on T_a was obtained, indicating that f_T is rather limited by the device intrinsic quantum and extrinsic capacitances than by an improved mobility due to reduced optical phonon scattering at low T_a. A noise analysis of the devices at T_a = 10 K reveals that the noise factor (NF) improvement at very low temperatures is related to the reduced Nyquist noise of all resistive transistor noise contributors. Since the main noise source in CNTFETs is the shot noise, NF remains comparatively high even at T_a = 10 K.

     

Equivalent magnetic noise in magnetoelectric Metglas/Pb(Mg1/3Nb2/3)O3‐PbTiO3 laminate composites

We have experimentally and theoretically investigated the equivalent magnetic noise in a magnetoelectric Metglas/ 0.7Pb(Mg_1/3Nb_2/3)O₃‐0.3PbTiO₃ laminate sensor unit by considering the constituent noise sources of dielectric loss (N_DE) and DC leakage resistance (N_R). In the low frequency range (f = 1 Hz), theory predicts that N_R dominates the noise charge (1.6 times larger than N_DE), with a 1 Hz noise of 9.1\;{\rm pt}/\sqrt {\rm Hz}. The experimental equivalent magnetic noise was 10.8\;{\rm pt}/\sqrt {\rm Hz}. This observed value is slightly higher than the predicted one, which might be due to an oversimplification of the theoretical model in terms of electrical charge amplifier and external vibration noise sources. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

掺Er光纤飞秒激光器中高信噪比载波包络位相偏移频率获取的实验研究

在实验上分析了掺Er光纤光学频率梳中激光器与一级放大器之间光纤长度、 光纤扰动以及放大器抽运功率对倍频程光谱和载波包络位相偏移频率(f₀)信噪比的影响. 通过系统优化, 实现了40 dB信噪比的f₀输出, 为f₀的长期锁定和光纤光学频率梳的实现提供了技术保障.     

Ni/Pb(Zr,Ti)O3/TbFe2层状复合材料的谐振磁电特性研究

采用化学镀和黏接法制备层状磁电复合材料Ni/PZT/TbFe₂,研究其磁电性能及谐振频率随Ni层厚度的变化情况. 结果表明:Ni/PZT/TbFe₂层状磁电复合材料与其他结构的磁电性能不同,其一阶弯曲谐振峰值和纵向谐振峰值都很大. 随着Ni层厚度的增加,Ni/PZT/TbFe₂层状磁电复合材料的一阶纵向谐振峰值逐渐增大. 结合实验数据和理论计算值得出了材料的一阶弯曲谐振频率fr1和一阶纵向谐振频率f 关键词： 磁电效应 正磁致伸缩 负磁致伸缩 谐振频率     

Isotopic effects on non-linearity, molecular radius and intermolecular free length

Computation of non-linearity parameter (B/A), molecular radius (r _m) and intermolecular free length (L _f) for H₂O, C₆H₆, C₆H₁₂, CH₃OH, C₂H₅OH and their deuterium-substituted compounds have been carried out at four different temperatures, viz., 293.15, 303.15, 313.15 and 323.15 K. The aim of the investigation is an attempt to study the isotopic effects on the non-linearity parameter and the physicochemical properties of the liquids, which in turn has been used to study their effect on the intermolecular interactions produced thereof.     

Mechanism of giant magnetoresistance in intermetallic compounds of rare-earth ions and actinides

Giant positive or negative magnetoresistance is calculated in a band model. The spectra of the band electrons in a two-sublattice antiferromagnetic intermetallic compound depend on the antiferromagnetism vector L(T,H). The metamagnetic transition to the ferromagnetic phase is accompanied by splitting with respect to the spin σ, displacement of the energy bands, and a decrease in the effective masses of the band electrons. This mechanism of giant negative magnetoresistance is also accompanied by an increase in the relaxation time τ_jσ. Scattering by chemical-bond fluctuations is considered as the main relaxation mechanism. Giant positive magnetoresistance results from a four-subband model of 4f and 5f intermetallic compounds. The electron effective masses m _jσ(J _jT ) of the (j,σ) bands increase with the mean angular momentum J _1T (T,H) of an ion in the jth sublattice of 4(5)f ions. The thermodynamics of such a four-sublattice model, the nonlinear magnetization and magnetoresistance curves, and the nonmonotonic dependence of the specific heat C _m(T,H) on the field H are calculated. Fiz. Tverd. Tela (St. Petersburg) 39, 1806–1814 (October 1997)     

Hartree–Fock and density functional theory study of remote substituent effects on heterolytic Fe―C bond energies of p‐G‐C6H4CH2Fe(CO)2(η5‐C5H5) and p‐G‐C6H4(H)(CN)CFe(CO)2(η5‐C5H5)

Knowledge of the strength of the metal–ligand bond breaking and formation is fundamental for an understanding of the thermodynamics underlying many important stoichiometric and catalytic organometallic reactions. Quantum chemical calculations at different levels of theory have been used to investigate heterolytic Fe―C bond energies of para‐substituted benzyldicarbonyl(η⁵‐cyclopentadienyl)iron, p‐G‐C₆H₄CH₂Fp [1, G = NO₂, CN, COMe, CO₂Me, CF₃, Br, Cl, F, H, Me, MeO, NMe₂; Fp = (η⁵‐C₅H₅)(CO)₂Fe], and para‐substituted α‐cyanobenzyldicarbonyl(η⁵‐cyclopentadienyl)iron, p‐G‐PANFp [2, PAN = C₆H₄CH(CN)]. The results show that BP86 and TPSSTPSS can provide the best price/performance ratio and more accurate predictions in the study of ΔH_het(Fe―C)'s. The good linear correlations [r = 0.98 (g, 1a), 0.99 (g, 2b)] between the substituent effects of heterolytic Fe―C bond energies [ΔΔH_het(Fe―C)'s] of series 1 and 2 and the differences of acidic dissociation constants (ΔpK_a) of C―H bonds of p‐G‐C₆H₄CH₃ and p‐G‐C₆H₄CH₂CN imply that the governing structural factors for these bond scissions are similar. And the excellent linear correlations [r = ?1.00 (g, 1c), ?0.99 (g, 2d)] between ΔΔH_het(Fe―C)'s and the substituent σ_p^? constants show that these correlations are in accordance with Hammett linear free energy relationships. The polar effects of these substituents and the basis set effects influence the accuracy of ΔH_het(Fe―C)'s. ΔΔH_het(Fe―C)'s(1, 2) follow the Capto‐dative Principle. The detailed knowledge of the factors that determine the Fp―C bond strengths would greatly aid in understanding reactivity patterns in many processes. Copyright © 2011 John Wiley & Sons, Ltd.     

Kinetic study on effect of novel cationic dimeric surfactants for the cleavage of carboxylate ester

Kinetic study has been performed to understand the reactivity of novel cationic gemini surfactants viz. alkanediyl‐α,ω‐bis(hydroxyethylmethylhexadecylammonium bromide) C₁₆‐s‐C₁₆ MEA, 2Br^? (where s = 4, 6) in the cleavage of p‐nitrophenyl benzoate (PNPB). Novel cationic gemini C₁₆‐s‐C₁₆ MEA, 2Br^? surfactants are efficient in promoting PNPB cleavage in presence of butane 2,3‐dione monoximate and N‐phenylbenzohydroxamate ions. Model calculation revealed that the higher catalytic effect of ethanol moiety of gemini surfactants (C₁₆H₃₃N⁺ C₂H₄OH CH₃ (CH₂)_S N⁺ C₂H₄OH CH₃C₁₆H₃₃, 2Br^?, s = 4, 6) is due to their higher binding capacity toward substrate. This is in line with finding that binding constants for novel series of cationic gemini surfactants are higher than conventional cationic gemini (C₁₆H₃₃N⁺(CH₃)₂(CH₂)_SN⁺(CH₃)₂C₁₆H₃₃, 2Br^?, s = 10, 12), cetyldimethylethanolammonium bromide and zwitterionic surfactants, i.e. C_nH_2n+1N⁺Me₂ (CH₂)₃ SO₃^? (n = 10; SB3‐10). The fitting of kinetic data was analyzed by the pseudophase model. Copyright © 2013 John Wiley & Sons, Ltd.     

A generalized edge of the wedge theorem

The edge of the wedge theorem is generalized to the case where one only assumes the existence and equality of the distribution boundary values off _±(z) and all their derivatives on some analytic curveC inR ⁿ . Heref _±(z) are holomorphic inR ⁿ ±iC, respectively, whereC is a convex cone, andC has its tangent vector inC at every point. Under these assumptions there exists an analytic continuationf(z) holomorphic in some complex neighbourhood of the double cone generated byC. A proof is also given of the connection between the existence of a distribution boundary value and the growth of the holomorphic function near the boundary.     

Steric effects on the mechanism of reaction of nucleophilic substitution of β‐substituted alkoxyvinyl trifluoromethyl ketones with four secondary amines

The kinetics of the reaction of β‐substituted β‐alkoxyvinyl trifluoromethyl ketones R¹O‐CR²?CH‐COCF₃ ( 1a – e ) [( 1a ), R¹?C₂H₅, R²?H; ( 1b ), R¹?R²?CH₃; ( 1c ), R¹?C₂H₅, R²?C₆H₅; ( 1d ), R¹?C₂H₅, R²?V^?pNO₂C₆H₄; ( 1e ), R¹?C₂H₅, R²?C(CH₃)₃] with four aliphatic amines ( 2a – d ) [( 2a ), (C₂H₅)₂NH; ( 2b ), (i‐C₃H₇)₂NH; ( 2c ), (CH₂)₅NH; ( 2d ), O(CH₂CH₂)₂NH] was studied in two aprotic solvents, hexane and acetonitrile. The least reactive stereoisomeric form of ( 1a – d ) was the most populated ( E‐s‐Z‐o‐Z ) form, whereas in ( 1e ), the more reactive form ( Z‐s‐Z‐o‐Z ) dominated. The reactions studied proceeded via common transition state formation whose decomposition occurred by ‘uncatalyzed’ and/or ‘catalyzed’ route. Shielding of the reaction centre by bulky β‐substituents lowered abruptly both k′ (‘uncatalyzed’ rate constant) and k″ (‘catalyzed’ rate constant) of this reaction. Bulky amines reduced k″ to a greater extent than k′ as a result of an additional steric retardation to the approach of the bulky amine to its ammonium ion in the transition state. An increase in the electron‐withdrawing ability of the β‐substituent increased ‘uncatalyzed’ k′ due to the acceleration of the initial nucleophile attack (k₁) and ‘uncatalyzed’ decomposition of transition state (k₂) via promoting electrophilic assistance (through transition state 8 ). The amine basicity determined the route of the reaction: the higher amine basicity, the higher k₃/k₂ ratio (a measure of the ‘catalyzed’ route contribution as compared to the ‘uncatalyzed’ process) was. ‘Uncatalyzed’ route predominated for all reactions; however in polar acetonitrile the contribution of the ‘catalyzed’ route was significant for amines with high pK_a and small bulk. Copyright © 2007 John Wiley & Sons, Ltd.     

Determination of optical nonlinearities in Cu(mpo)2 by Z-scan technique

The optical nonlinearities of Cu(mpo)₂ [formula = C₁₀H₈N₂CuO₂S₂] complex have firstly been investigated by using the Z-scan technique with a nanosecond-pulsed Nd:YAG laser at its second harmonic (532 nm) radiation. The nonlinear optical absorption and refraction coefficients of Cu(mpo)₂ have been measured with the different on-axial peak irradiances I ₀ at the waist ranging from 0.48 to 5.66 GW/cm². The nonlinear transmittance characteristics exhibit the near resonant two-photon absorption (TPA) at 532 nm and are explained by a population redistribution model. The nonlinear absorption originates from the near resonant TPA while the mechanism of the nonlinear refraction is the near resonant TPA transition enhancement. The linear increasing dependences of the optical nonlinearities on the incident irradiance arise from the population redistribution due to the near resonant TPA.     

Capacity of Multivariate Channels with Multiplicative Noise: Random Matrix Techniques and Large-N Expansions (2)

We study memoryless, discrete time, matrix channels with additive white Gaussian noise and input power constraints of the form Y i = ∑ _j H _ij X _j + Z _i , where Y _i , X _j and Z _i are complex, i = 1… m, j = 1… n, and H is a complex m× n matrix with some degree of randomness in its entries. The additive Gaussian noise vector is assumed to have uncorrelated entries. Let H be a full matrix (non-sparse) with pairwise correlations between matrix entries of the form E[H ik H ^* jl] = 1/n C ij D kl, where C, D are positive definite Hermitian matrices. Simplicities arise in the limit of large matrix sizes (the so called large-n limit) which allow us to obtain several exact expressions relating to the channel capacity. We study the probability distribution of the quantity f(H) = log (1+PH ^† SH) . S is non-negative definite and hermitian, with TrS = n and P being the signal power per input channel. Note that the expectation E[f(H)], maximised over S, gives the capacity of the above channel with an input power constraint in the case H is known at the receiver but not at the transmitter. For arbitrary C, D exact expressions are obtained for the expectation and variance of f(H) in the large matrix size limit. For C = D = I, where I is the identity matrix, expressions are in addition obtained for the full moment generating function for arbitrary (finite) matrix size in the large signal to noise limit. Finally, we obtain the channel capacity where the channel matrix is partly known and partly unknown and of the form α; I+ β H, α,β being known constants and entries of H i.i.d. Gaussian with variance 1/n. Channels of the form described above are of interest for wireless transmission with multiple antennae and receivers.     

Kinetics and mechanism of the reaction of alkoxymethylidene malonate and malononitrile with hydrazines and anilines

The kinetics and mechanism of the nucleophilic vinylic substitution of dialkyl (alkoxymethylidene)malonates (alkyl: methyl, ethyl) and (ethoxymethylidene)malononitrile with substituted hydrazines and anilines R¹–NH₂ (R¹: (CH₃)₂N, CH₃NH, NH₂, C₆H₅NH, CH₃CONH, 4‐CH₃C₆H₄SO₂NH, 3‐ and 4‐X‐C₆H₄; X: H, 4‐Br, 4‐CH₃, 4‐CH₃O, 3‐Cl) were studied at 25 °C in methanol. It was found that the reactions with all hydrazines (the only exception was the reaction of (ethoxymethylidene)malononitrile with N,N‐dimethylhydrazine) showed overall second‐order kinetics and k_obs were linearly dependent on the hydrazine concentration which is consistent with the rate‐limiting attack of the hydrazine on the double bond of the substrate. Corresponding Brønsted plots are linear (without deviating N‐methyl and N,N‐dimethylhydrazine), and their slopes (β_Nuc) gradually increase from 0.59 to 0.71 which reflects gradually increasing order of the C–N bond formed in the transition state. The deviation of both methylated hydrazines is probably caused by the different site of nucleophilicity/basicity in these compounds (tertiary/secondary vs. primary nitrogen). A somewhat different situation was observed with the anilines (and once with N,N‐dimethylhydrazine) where parabolic dependences of the kinetics gradually changing to linear dependences as the concentration of nucleophile/base increases. The second‐order term in the nucleophile indicates the presence of a steady‐state intermediate ‐ most probably T^±. Brønsted and Hammett plots gave β_Nuc = 1.08 and ρ = ?3.7 which is consistent with a late transition state whose structure resembles T^±. Copyright © 2013 John Wiley & Sons, Ltd.     

Density functional theory study of substituent effects on gas‐phase heterolytic Fe–O and Fe–S bond energies of m‐G‐C6H4OFe(CO)2(η5‐C5H5) and m‐G‐C6H4SFe(CO)2(η5‐C5H5)

The knowledge of accurate bond strengths is a fundamental basis for a proper analysis of chemical reaction mechanisms. Quantum chemical calculations at different levels of theory have been used to investigate heterolytic Fe–O and Fe–S bond energies of (meta‐substituted phenoxy)dicarbonyl(η⁵‐cyclopentadienyl) iron [m‐G‐C₆H₄OFp ( 1 )] and (meta‐substituted benzenethiolato)dicarbonyl(η⁵‐cyclopentadienyl) iron [m‐G‐C₆H₄SFp ( 2 )] complexes. In this study, Fp is (η⁵‐C₅H₅)Fe(CO)₂, and G is NO₂, CN, COMe, CO₂Me, CF₃, Br, Cl, F, H, Me, MeO, and NMe₂. The results show that Tao–Perdew–Staroverov–Scuseria and Becke's power‐series ansatz from 1997 with dispersion corrections functionals can provide the best price/performance ratio and accurate predictions of ΔH_het(Fe–O)'s and ΔH_het(Fe–S)'s. The excellent linear free energy relations [r = 1.00 (g, 1e), 1.00 (g, 2b)] among the ΔΔH_het (Fe–O)'s and δΔG⁰ of O?H bonds of m‐G‐C₆H₄OH or ΔΔH_het(Fe–S)'s and ΔpK_a's of S?H bonds of m‐G‐C₆H₄SH imply that the governing structural factors for these bond scissions are similar. And, the linear correlations [r = ?0.97 (g, 1 g), ?0.97 (g, 2 h)] among the ΔΔH_het (Fe–O)'s or ΔΔH_het(Fe–S)'s and the substituent σ_m constants show that these correlations are in accordance with Hammett linear free energy relationships. The inductive effects of these substituents and the basis set effects influence the accuracy of ΔH_het(Fe–O)'s or ΔH_het(Fe–S)'s. The ΔΔH_het(Fe–O)'s(g) (1) and ΔΔH_het(Fe–S)'s(g)(2) follow the capto‐dative Principle. The substituent effects on the Fe–O bonds are much stronger than those on the less polar Fe–S bonds. Insight from this work may help the design of more effective catalytic processes. Copyright © 2016 John Wiley & Sons, Ltd.