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41.
Possible molecular mechanisms of the gas-phase ion/molecule reaction of VO2+ in its lowest singlet and triplet states (1A1/3A' ') with propyne have been investigated theoretically by density functional theory (DFT) methods. The geometries, energetic values, and bonding features of all stationary and intersystem crossing points involved in the five different reaction pathways (paths 1-5), in both high-spin (triplet) and low-spin (singlet) surfaces, are reported and analyzed. The oxidation reaction starts by a hydrogen transfer from propyne molecule to the vanadyl complex, followed by oxygen migration to the hydrocarbon moiety. A hydride transfer process to the vanadium atom opens four different reaction courses, paths 1-4, while path 5 arises from a hydrogen transfer process to the hydroxyl group. Five crossing points between high- and low-spin states are found: one of them takes place before the first branching point, while the others occur along path 1. Four different exit channels are found: elimination of hydrogen molecule to yield propynaldehyde and VO+ (1Sigma/3Sigma); formation of propynaldehyde and the moiety V-(OH2)+; and two elimination processes of water molecule to yield cationic products, Prod-fc+ and Prod-dc+ where the vanadium atom adopts a four- and di-coordinate structure, respectively. 相似文献
42.
Cuadros-Rodríguez L Bagur-González MG Sánchez-Viñas M González-Casado A Gómez-Sáez AM 《Journal of chromatography. A》2007,1158(1-2):33-46
Calibration is an operation whose main objective is to know the metrological status of a measurement system. Nevertheless, in analytical sciences, calibration has special connotations since it is the basis to do the quantification of the amount of one or more components (analytes) in a sample, or to obtain the value of one or more analytical parameters related with that quantity. Regarding this subject, the aim of analytical calibration is to find an empiric relationship, called measurement function, which permits subsequently to calculate the values of the amount (x-variable) of a substance in a sample, from the measured values on it of an analytical signal (y-variable). In this paper, the metrological bases of analytical calibration and quantification are established and, the different work schemes and calibration methodologies, which can be applied depending on the characteristic of the sample (analyte+matrix) to analyse, are distinguished and discussed. Likewise, the different terms and related names are clarified. A special attention has been paid to those analytical methods which use separation techniques, in relation with its effect on calibration operations and later analytical quantification. 相似文献
43.
44.
We report on the structure and bonding in the title iron(III) complexes, containing the tris[(N'-tert-butylureayl)-N-ethyl]amine ligand, with density functional theory techniques. In agreement with the experimental data, a high-spin electronic state is favored for all of the systems we considered. H bonds between the terminal oxo and hydroxo ligands and NH groups present in the organic ligand coordinated to the metal have a remarkable effect on the overall coordination geometry. In fact, the structure of model complexes without H bonds shows shorter Fe-O bond lengths. This is a consequence of the ability of the H bonds to stabilize a remarkable amount of electron density localized on the terminal oxo and hydroxo ligands. Energy analysis indicates that each H bond stabilizes the nonheme complexes by roughly 35 kJ/mol. Molecular orbital analysis indicates a reduction of two Fe-O bonding electrons on going from a complex with a terminal oxo ligand to a complex with a terminal hydroxo ligand. This reduction in the number of bonding electrons is also supported by frequency analysis. 相似文献
45.
为实现三维光存储中折射率失配引起的球差补偿,建立了光学存储系统模型,获得了折射率失配引起的波前偏差函数与存储深度的表达式.采用泽尔尼克循环多项式对波前偏差函数进行补偿展开.在双光子荧光和单光子共焦荧光读出方式下,均可获得读出荧光强度与存储深度的关系:在折射率失配引起的球差未得到补偿矫正的情况下,存储深度在200 μm左右读出荧光强度基本上下降为零;当折射率失配引起的初级球差被补偿矫正后,读出荧光强度随存储深度的下降得到较好改善;当折射率失配引起的二级球差被补偿矫正后,存储深度在1 mm内存储点强度随深度基本上没有明显地变化.并且对像差补偿方法进行了具体地分析. 相似文献
46.
Malgorzata Frik Dr. Josefina Jiménez Ismael Gracia Prof. Larry R. Falvello Sarya Abi‐Habib Karina Suriel Prof. Theodore R. Muth Prof. María Contel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(12):3659-3674
The reaction of new dinuclear gold(I) organometallic complexes containing mesityl ligands and bridging bidentate phosphanes [Au2(mes)2(μ‐LL)] (LL=dppe: 1,2‐bis(diphenylphosphano)ethane 1 a , and water‐soluble dppy: 1,2‐bis(di‐3‐pyridylphosphano)ethane 1 b ) with Ag+ and Cu+ lead to the formation of a family of heterometallic clusters with mesityl bridging ligands of the general formula [Au2M(μ‐mes)2(μ‐LL)][A] (M=Ag, A=ClO4?, LL=dppe 2 a , dppy 2 b ; M=Ag, A=SO3CF3?, LL=dppe 3 a , dppy 3 b ; M=Cu, A=PF6?, LL=dppe 4 a , dppy 4 b ). The new compounds were characterized by different spectroscopic techniques and mass spectrometry The crystal structures of [Au2(mes)2(μ‐dppy)] ( 1 b ) and [Au2Ag(μ‐mes)2(μ‐dppe)][SO3CF3] ( 3 a ) were determined by a single‐crystal X‐ray diffraction study. 3 a in solid state is not a cyclic trinuclear Au2Ag derivative but it gives an open polymeric structure instead, with the {Au2(μ‐dppe)} fragments “linked” by {Ag(μ‐mes)2} units. The very short distances of 2.7559(6) Å (Au? Ag) and 2.9229(8) Å (Au? Au) are indicative of gold–silver (metallophilic) and aurophilic interactions. A systematic study of their luminescence properties revealed that all compounds are brightly luminescent in solid state, at room temperature (RT) and at 77 K, or in frozen DMSO solutions with lifetimes in the microsecond range and probably due to the self‐aggregation of [Au2M(μ‐mes)2(μ‐LL)]+ units (M=Ag or Cu; LL=dppe or dppy) into an extended chain structure, through Au? Au and/or Au? M metallophilic interactions, as that observed for 3 a . In solid state the heterometallic Au2M complexes with dppe ( 2 a – 4 a ) show a shift of emission maxima (from ca. 430 to the range of 520‐540 nm) as compared to the parent dinuclear organometallic product 1 a while the complexes with dppy ( 2 b–4 b ) display a more moderate shift (505 for 1 b to a max of 563 nm for 4 b ). More importantly, compound [Au2Ag(μ‐mes)2(μ‐dppy)]ClO4 ( 2 b ) resulted luminescent in diluted DMSO solution at room temperature. Previously reported compound [Au2Cl2(μ‐LL)] (LL dppy 5 b ) was also studied for comparative purposes. The antimicrobial activity of 1–5 and Ag[A] (A=ClO4?, SO3CF3?) against Gram‐positive and Gram‐negative bacteria and yeast was evaluated. Most tested compounds displayed moderate to high antibacterial activity while heteronuclear Au2M derivatives with dppe ( 2 a – 4 a ) were the more active (minimum inhibitory concentration 10 to 1 μg mL?1). Compounds containing silver were ten times more active to Gram‐negative bacteria than the parent dinuclear compound 1 a or silver salts. Au2Ag compounds with dppy ( 2 b , 3 b ) were also potent against fungi. 相似文献
47.
In this paper we test for the presence of bubbles in the Nasdaq stock market index over the period 1994–2003 applying fractional integration techniques and allowing for structural breaks and non-linear adjustments of prices to dividends. The results show a significant structural break in 1998 for all model specifications and data periodicity. Furthermore, we do not find evidence of asymmetric adjustment of prices to dividends when using M-TAR and TAR models. The evidence of bubbles varies depending on the data periodicity and model specification used in the analysis. Finally, the results show persistent deviations of stock prices to dividends in all cases considered, though we only find evidence of bubbles in the Nasdaq index when using weekly data for the time period after June 1998. 相似文献
48.
Barth S Jimenez-Diaz R Samà J Prades JD Gracia I Santander J Cane C Romano-Rodriguez A 《Chemical communications (Cambridge, England)》2012,48(39):4734-4736
Simultaneous localized growth and device integration of inorganic nanostructures on heated micromembranes is demonstrated for single crystalline germanium and tin oxide nanowires. Fully operating CO gas sensors prove the potential of the presented approach. With this simple CMOS compatible technique, issues of assembly, transfer and contact formation are addressed. 相似文献
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50.
Philippe Blanchard José M. Gracia‐Bondiacute;a Joseph C. Várilly 《International journal of quantum chemistry》2012,112(4):1134-1164
Forty‐five years after the point de départ [Hohenberg and Kohn, Phys Rev, 1964, 136, B864] of density functional theory, its applications in chemistry and the study of electronic structures keep steadily growing. However, the precise form of the energy functional in terms of the electron density still eludes us—and possibly will do so forever [Schuch and Verstraete, Nat Phys, 2009, 5, 732]. In what follows we examine a formulation in the same spirit with phase space variables. The validity of Hohenberg–Kohn–Levy‐type theorems on phase space is recalled. We study the representability problem for reduced Wigner functions, and proceed to analyze properties of the new functional. Along the way, new results on states in the phase space formalism of quantum mechanics are established. Natural Wigner orbital theory is developed in depth, with the final aim of constructing accurate correlation‐exchange functionals on phase space. A new proof of the overbinding property of the Müller functional is given. This exact theory supplies its home at long last to that illustrious ancestor, the Thomas–Fermi model. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012 相似文献