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71.
A density functional theory investigation on a series of sandwich-type transition metal complexes [(CBO)n]2M (n=4–6; M=transition metals) with carbon boronyls (CBO)n as effective aromatic ligands has been presented in this work at B3LYP level. The ground-states of these complexes possess staggered Dnd symmetries, while the corresponding eclipsed Dnh structures exist as transition states with slightly higher energies (within 5.8 kJ/mol). Carbon boronyl complexes [(CBO)n]2M are confirmed to be much more stable than their boron carbonyl isomers [(BCO)n]2M, which, on the other hand, take eclipsed ground-states with Dnh symmetries. The carbon boronyl complexes [(BCO)n]2M proposed in this work parallelize the well-known sandwich-type hydrocarbon complexes [CnHn]2M in coordination chemistry with boronyl groups –BO isolobal to –H atoms in corresponding ligands. 相似文献
72.
A novel mixed valent tellurium oxide, SrTe3O8, has been synthesized and its crystal structure was determined ab initio from powder X-ray diffraction data. This oxide, which crystallizes in a tetragonal unit-cell, P42/m space group, with very close a and c cell parameters (6.8257(1) and 6.7603(1) Å, respectively), exhibits a very original structure built up of corner-sharing TeO6 (Te6+) octahedra and Te2O8 (Te4+) twin-pyramidal units. The latter ones form [Te3O8]∞ chains running along the [001] and the [110] directions. Besides the four sided tunnels where the Sr2+ cations are located, there are very large four sided tunnels running along the c-axis which are obstructed by the electronic lone pairs of the Te4+ cations. 相似文献
73.
Some K2O-TiO2-GeO2 glasses with a large amount of TiO2 contents (15-25 mol%) such as 25K2O-25TiO2-50GeO2 have been prepared, and their electronic polarizability, Raman scattering spectra, and crystallization behavior are examined to clarify thermal properties and structure of the glasses and to develop new nonlinear optical crystallized glasses. It is proposed that the glasses consist of the network of TiO6 and GeO4 polyhedra. The glasses show large optical basicities of Λ=0.88-0.92, indicating the high polarizabity of TiOn (n=4-6) polyhedra in the glasses. K2TiGe3O9 crystals are formed through crystallization in all glasses prepared in the present study. In particular, 20K2O-20TiO2-60GeO2 glass shows bulk crystallization and 18K2O-18TiO2-64GeO2 glass exhibits surface crystallization giving the c-axis orientation. The crystallized glasses show second harmonic generations (SHGs), and it is suggested that the distortion of TiO6 octahedra in K2TiGe3O9 crystals induces SHGs. 相似文献
74.
An intelligent, automatic system based on an array of non-specific-response chemical sensors was developed. As a great amount of information is required for its correct modelling, we propose a system generating it itself. The sequential injection analysis (SIA) technique was chosen as it enables the processes of training, calibration, validation and operation to be automated simply. Detection was carried out using an array of potentiometric sensors based on PVC membranes of different selectivity. The diluted standard solutions needed for system learning and response modelling are automatically prepared from more concentrated standards. The electrodes used were characterised with respect to one and two analytes, by means of high-dimensionality calibrations, and the response surface of each was represented; this characterisation enabled an interference study of great practical utility. The combined response was modelled by means of artificial neural networks (ANNs), and thus it was possible to obtain an automated electronic tongue based on SIA. In order to identify the ANN which provided the best model of the electrode responses, some of the network's parameters were optimised and its usefulness in determining NH4+, K+ and Na+ ions in synthetic samples was then tested. Finally, it was used to determine these ions in commercial fertilisers, the obtained results being compared with reference methods. 相似文献
75.
某些离解能、电子亲合能等的G2计算与评价 总被引:1,自引:1,他引:1
PoPle及其合作者创立的Gaussian再简称GZ)理论[‘-’],以其相对可靠的化学精度和相应较小的计算量已经引起了实验和理论化学家们的广泛关注问.p。ple等人在他们的GZ文章中强调了GZ的理论计算结果在研究离解能等化学问题中与精确实验数据之间的偏差普遍不大于全8.狄J规厂‘.我们近期的研究表明*’1,*2和优(*则在计算一般化学反应能量中,绝大多数情况下,分别都能保证结果与实验偏差在全8.4和士13kJ·mol‘以内.近年来,已有大量的研究工作表明,GZ的理论结果已广泛用于未知实验数据的预测、已有实验数据的评价和修正等… 相似文献
76.
A template synthesis procedure yielded [Ni(HL1)NH3]I, where HL1 is the monoanion of the terdentate ONN benzoylacetone S-methylisothiosemicarbazone ligand. The reaction of this complex with an excess of NH4NCS, pyridine, or hydrazine resulted in the complexes [Ni(HL1)(NH3)NCS] and [Ni(L1)A] (A = Py, N2H4). The monoanionic form of the ligand is obtained by deprotonation of the enolic form of the benzoylacetone moiety, whereas the dianion is formed by additional deprotonation of the terminal NH2 group. Finally, the reaction of [Ni(HL1)NH3]I with salicyladehyde produced the NiL2 complex in which L2 stands for the dianion of the ONNO ligand N(1)-2-butylidene-4-oxo-4-phenyl-N(4)-salicylidene-S-methylisothiosemicarbazide. All complexes are diamagnetic and have a square-planar configuration, except for [Ni(HL1)(NH3)NCS], for which te data of i.r. spectra suggest a square-pyramidal structure. The electronic absorption spectra of the ethanolic solutions of all complexes are characteristic of typical square-planar coordination of nickel(II). 相似文献
77.
Nobuyuki Akai Satoshi Kudoh Masao Takayanagi Munetaka Nakata 《Journal of photochemistry and photobiology. A, Chemistry》2002,150(1-3):93-100
Rotational isomerization of 2-chlorobenzaldehyde in low-temperature rare-gas matrices has been investigated by vibrational and electronic spectroscopies with aids of the density functional theory (DFT) and configuration interaction single (CIS) calculations. Infrared spectrum of the less stable O-cis isomer, produced from the more stable O-trans isomer upon UV irradiation, is measured with an FT-IR spectrophotometer. The enthalpy difference between the O-cis and O-trans isomers is estimated to be 9.7±0.2 kJ mol−1 from the temperature dependence of the infrared band intensities. Analyses of the infrared and electronic absorption spectral changes after UV irradiation and the phosphorescence spectra measured at various excitation wavelengths suggest that the rotational isomerization occurs via the intersystem crossing from S1 to T1. 相似文献
78.
Corrado Di Natale Manuela Zude-SasseAntonella Macagnano Roberto PaolesseBernd Herold Arnaldo D’Amico 《Analytica chimica acta》2002,459(1):107-117
Visual aspect and aroma are among the most important features of fruit that determine consumer preferences. Electronic nose and spectroscopic techniques have shown positive results in evaluating some basic analytical parameters of fruit and global features such as the cultivar.In this paper, we illustrate and discuss a study aimed at evaluating the improvement derived by the fusion of visible spectra and electronic nose data. These experiments were performed on a population of yellow peaches belonging to two cultivars. Each sample was measured by visible optical spectroscopy and by electronic nose. In addition, a number of reference parameters were also measured by conventional destructive methodologies.Collected data were analysed individually and then fused together in order to classify the two cultivars and to estimate the reference parameters. Data fusion was performed building the outer product matrix for each measurement. The set of matrices was then successively unfolded and analysed by conventional chemometrics tools.Results were improved using outer products, for instance in classification average percentage errors of 25, 10, and 7 for electronic nose, spectra, and outer product, respectively was achieved. Regression analysis provides the evidence of a substantial orthogonal appearance of the datasets, which offer former hidden information on fruit classification. 相似文献
79.
INDO方法研究了C70R2(R=OH,CH3)4种异构体的结构和稳定性,表明1,9-C70(OH)2比7,8-C70(OH)2稳定,两者能量差为38.5kJ/mol,而7,8-C70(CH3)2比1,9-C70(CH3)2能量低23.0kJ/mol.以优化构型为基础,对C70R2(R=OH,CH3)的电子光谱进行了理论预测. 相似文献
80.
Ab initio molecular orbital calculations using both minimal and extended basis sets have been applied to two isoelectronic sets of molecules. One set corresponds to the 18 electron species H3NO, H3CO– and H3COH while the second set contains the 42 electron fluorinated molecules F3NO, F3CO– and F3COH. The geometries of these molecules have been optimized, using both the minimal STO-3G and the extended 4-31G basis sets. These comparative calculations reveal that the 4-31G basis produced structural parameters in much better agreement with experiment. The effect of includingd-orbitals in the basis set was also investigated. For the fluorinated oxides it has been found that the optimized 4-31G structures were only slightly altered by the addition ofd-orbitals. For H3NO, on the other hand, the inclusion ofd-orbitals considerably shortens the N-O bond distance. Both H3NO and CF3OH, which are unknown experimentally, are theoretically predicted to be capable of existence. The electronic structures of these molecules have also been examined using electronic partitioning according to the Mulliken scheme. 相似文献