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91.
Geometries and electronic structures of W4 and W clusters were studied by use of density functional methods B3LYP, B3P86, B3PW91, BHLYP, BLYP, and MPW1PW91. The calculated results indicate that the three‐dimensional structure of singlet state with either D2d symmetry (B3LYP, B3P86, B3PW91, BLYP, and MPW1PW91) or C2v symmetry (BHLYP) is the ground state for the W4 cluster. For the W cluster, the doublet state is preferred, and the most stable structure is also 3D with either D2d symmetry (B3LYP, B3PW91, BHLYP, BLYP) or C2v symmetry (B3P86 and MPW1PW91). The calculated electron affinity at B3P86 gives the best performance compared with experiment. For the dissociation channel, W + W3 is suggested to be the possible route for the W4 cluster. For the W cluster, W + W is the most likely route for dissociation, in agreement with experiment. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 相似文献
92.
I. Kuselman 《Accreditation and quality assurance》1998,3(3):131-133
It is argued that results of uncertainty calculations in chemical analysis should be taken into consideration with some caution
owing to their limited generality. The issue of the uncertainty in uncertainty estimation is discussed in two aspects. The
first is due to the differences between procedure-oriented and result-oriented uncertainty assessments, and the second is
due to the differences between the theoretical calculation of uncertainty and its quantication using the validation (experimental)
data. It is shown that the uncertainty calculation for instrumental analytical methods using a regression calibration curve
is result-oriented and meaningful only until the next calibration. A scheme for evaluation of the uncertainty in uncertainty
calculation by statistical analysis of experimental data is given and illustrated with examples from the author's practice.
Some recommendations for the design of corresponding experiments are formulated. 相似文献
93.
Reliable, traceable and comparable measurements provide the rational basis for evaluation of the quality of a result and
the starting point for recognized laboratory accreditation in any national area. Modern medical diagnostics and treatment
involve rapidly rising numbers and types of clinical laboratory measurements, that are reliable. Therefore, the basic principles
to be followed to assure the traceability of clinical measurements as required by the Romanian Laws of Metrology are reviewed.
Main sources affecting the quality of the unbroken chain of calibrations that relate the measurements back to appropriate
measurement standards are discussed. Examples of how to achieve traceable measurements in clinical laboratories are presented.
Details of specific uses of reference materials, measuring instruments and standard measurement methods are also discussed.
Received: 8 January 1998 · Accepted: 21 April 1998 相似文献
94.
S. Küppers 《Accreditation and quality assurance》1997,2(1):30-35
Any analytical data is used to provide information about a sample. The "possible error" of the measurement can be of extreme
importance in order to have complete information. The measurement uncertainty concept is a way to achieve quantitative information
about this "possible error" using an estimation procedure. On the basis of the analytical result, the chemist makes a decision
on the next step of the development process. If the uncertainty is unknown, the information is not complete; therefore this
decision might be impossible. The major problem for the in-process control (IPC) procedure is that not only the repeatability
but also the intermediate precision (which expresses the variations within laboratories related to different days, different
analysts, different equipment, etc.) has to be good enough to make a decision. Unfortunately, the statistical information
achieved from one single analytical run only gives information about the repeatability. This paper shows that the estimation
of the measurement uncertainty for IPC is a way to solve the problem and gives the necessary information about the quality
of the procedure. An example demonstrates that an estimate of uncertainty based on the standard deviations of an analytical
method gives a value similar to one based on the standard deviations obtained from a control chart. Therefore, the estimation
is both a very useful and also a very cost-effective tool. Though measurement uncertainty cannot replace validation in general,
it is a viable alternative to validation for all methods that will never be used routinely.
Received: 24 May 1996 Accepted: 10 August 1996 相似文献
95.
采用重量-容量法制备丙酮中除虫脲溶液标准物质。准确称量国家二级标准物质除虫脲溶解到色谱纯丙酮中,通过A级容量瓶定容至500 mL,摇匀后分装到2 mL安瓿瓶内共460瓶,每瓶为1 mL,保持低温迅速封口,配制过程中室温保持在(20±2)℃。采用液相色谱法进行均匀性、稳定性检验和定值结果验证。从样品中随机抽取16瓶进行均匀性检验,经F检验表明,在95%的置信区间范围内该标准物质均匀性良好;采用t检验对标准物质稳定性进行检验,标准物质在12月内稳定性良好。对该标准物质的不确定度进行了评定,研制的丙酮中除虫脲溶液标准物质定值结果为100μg/mL,相对扩展不确定度为2%(k=2)。结果表明,该标准物质均匀性与稳定性良好,量值准确,可用于日常分析检测中的方法评价和仪器校准。 相似文献
96.
热塑性塑料熔体质量流动速率测量不确定度的评定 总被引:1,自引:0,他引:1
以聚乙烯为例讨论了热塑性塑料熔体质量流动速率测量不确定度的来源,依据JJF 1059-1999对熔体流动速率测试过程中的测量不确定度分量进行了分析和评定。7149型聚乙烯熔体质量流动速率测量结果的扩展不确定度为0.096 g/(10 m in)。 相似文献
97.
A procedure for estimation of measurement uncertainty of routine pH measurement (pH meter with two-point calibration, with
or without automatic temperature compensation, combination glass electrode) based on the ISO method is presented. It is based
on a mathematical model of pH measurement that involves nine input parameters. Altogether 14 components of uncertainty are
identified and quantified. No single uncertainty estimate can be ascribed to a pH measurement procedure: the uncertainty of
pH strongly depends on changes in experimental details and on the pH value itself. The uncertainty is the lowest near the
isopotential point and in the center of the calibration line and can increase by a factor of 2 (depending on the details of
the measurement procedure) when moving from around pH 7 to around pH 2 or 11. Therefore it is necessary to estimate the uncertainty
separately for each measurement. For routine pH measurement the uncertainty cannot be significantly reduced by using more
accurate standard solutions than ±0.02 pH units – the uncertainty improvement is small. A major problem in estimating the
uncertainty of pH is the residual junction potential, which is almost impossible to take rigorously into account in the framework
of a routine pH measurement.1
Received: 11 August 2001 Accepted: 22 February 2002 相似文献
98.
The authors study rotational hypersurfaces with constant Gauss-Kronecker curvature in Rn. They solve the ODE associated with the generating curve of such hypersurface using integral expressions and obtain several geometric properties of such hypersurfaces. In particular, they discover a class of non-compact rotational hypersurfaces with constant and negative Gauss-Kronecker curvature and finite volume, which can be seen as the higher-dimensional generalization of the pseudo-sphere. 相似文献
99.
不确定金融是不确定理论在现代金融领域的一种应用,在解决金融问题中发挥着越来越重要的作用。而利率是一个重要的经济指标,经常受到一些不确定因素的影响,在研究期权定价时,有必要考虑浮动利率。本文提出了一种新的不确定指数Ornstein-Uhlenbeck过程模型,假设利率服从不确定均值回复过程,研究了期权定价问题,运用α-轨道方法,分别推导了亚式看涨期权和看跌期权定价公式。最后,设计了计算期权价格的数值算法,并给出数值算例。 相似文献
100.
It is shown how to represent algebraically all functions that have a zero sum on all -dimensional subspaces ofPG(n,q) or ofAG(n,q). In this way one can calculate the dimensions of related codes, or one can represent interesting sets of points by functions. 相似文献