Comparison of localization and delocalization indices obtained with Hartree-Fock and conventional correlated methods: effect of Coulomb correlation

Atomic populations and localization [lambda(A)] and delocalization [delta(A,B)] indices (LIs and DIs) are calculated for a large set of molecules at the Hartree-Fock (HF), MP2, MP4(SDQ), CISD, and QCISD levels with the 6-311++G(2d,2p) basis set. The HF method and the conventional correlation methods [MP2, MP4(SDQ), CISD, and QCISD] yield distinct sets of LIs and DIs. Yet, within the four conventional correlation methods the differences in atomic populations and LIs and DIs are small. Relative to HF, the conventional correlation methods [MP2, MP4(SDQ), CISD, QCISD] yield virtually the same LIs and DIs for molecules with large charge separations while LIs and DIs that differ significantly from the HF values--the LIs are increased and DIs decreased--are obtained for bonds with no or small charge separations. Such is the case in the archetypal homopolar molecules HC(triple bond)CH, H2C=CH2, CH3-CH3, and "protonated cyclopropane" C(3)H(7) (+), in which case the bonding may be atypical. Relative to HF, the typical effect of the conventional correlation methods is to decrease the DI between atoms.     

流动注入吸附溶出—催化极谱氢波分析痕量铂

本文叙述一种流动注入吸附溶出一催化极谱测定痕量铂的新技术,它集中了溶出法、催化波和流动注入的优点,达到非常高的灵敏度和分析速度。实验给出了最佳载液组成、流速、注入体积、吸附富集电位和吸附时间等因素。本方法成功地进行了多种铂络合物、矿样和生物样品分析。     

氧极谱催化波法测定二苯胺

本文报道一种极谱测定二苯胺的新方法,它是基于二苯胺引起的氧极谱催化波.这个氧极谱催化波是由于二苯胺催化了电生超氧离子O_2~(-)的歧化反应产生的.本方法简单方便,有良好选择性.应用本方法测定了化工原料二苯胺的含量,结果令人满意.     

钍-铬天青S的极谱吸附波

在0.12moL/L乙酸铵-0.05%磺基水杨酸-0.15%乙醇,pH5.8～6.0的条件下,钍与铬天青S在-0.45W(vs SCE)有一良好的导数极谱波。钍浓度在0～0.4μg/mL范围内与波高呈直线关系。     

线性扫描极谱法测定微量肉桂酸

在 1mol·L-1HOAc NaOAc介质中 (pH =3.6 ) ,肉桂酸有一还原峰 ,其峰电位为 - 1.4 7V(vs.SCE)。峰电流与肉桂酸浓度在 2 .0× 10 -5～ 8.0× 10 -4 mol·L-1之间呈线性关系 (r =0 .9989) ,检出限为 1.0× 10 -5mol·L-1。该法应用于肉桂酸含量的测定 ,结果满意 ,并对肉桂酸的电化学性质进行了研究     

极谱杂多酸吸附波测定合金中硅

在pH2—4的盐酸介质中,硅(Ⅳ)、锑(Ⅲ)与铝(Ⅵ)形成三元杂多酸,此三元杂多酸在0.4mol/L的HCl中能迅速在滴汞电极上还原而产生灵敏的极谱电流。其峰电位为-0.30V(vs.SCE)。测定下限是8×10~(-8)mol/L。     

Evanescent fluorobiosensor for the detection of polyaromatic hydrocarbon based on DNA intercalation

A flow-injection analysis (FIA) system coupled with an evanescent wave (EW) Biosensor employing total internal reflection of fluorescence radiation (TIRF) for the detection of polyaromatic hydrocarbon that intercalates into DNA is reported. A highly fluorescent intercalator, “ethidium bromide,” has been used as the reference compound for detection. The EW Biosensor was developed according to the procedure described earlier (1,2). Data on the analysis of Naphthalene, 3-methy cholanthrene, 7,12-dimethylbenz(a)anthracene, 1,2-benzanthracene, and some standard reference materials supplied by the National Institute of Standards and Technology are reported. The relative ability of the polyaromatic hydrocarbon to displace ethidium bromide, based on the relative binding ratio, is found to be on the order of 7,12-dimethylbenz[a]anthracene > 3-methylcholanthrene > 1,2-benzanthracene > napthalene.     

络合吸附体系吸附性的研究

本文论述了研究络合吸附体系吸附性的重要意义,较详细地讨论了各种方法,包括微分电容曲线法、交流极谱法和计时电量法等在吸附性研究和吸附量测定中的应用。     

Fields as Kolmogzrov flows

It is widely recognized that for highly unstable dynamical systems there exists a fundamental limitation on predictability and determinism. An important class of such highly unstable systems is the class of K-flow, which is further characterized by the existence of time-asymmetric objects in the form of K-partition. Our recent approach to the problem of irreversibility has shown that when the implications of the limitation on determinism arising from strong form of instability and those of the existence of K-partition are consistently taken into account, one is naturally led from the physically unrealizable deterministic evolution of phase points to an entropy-increasing stochastic Markovian evolution. Furthermore, this transition is not the result of extraneously imposed coarse graining and/or approximation schemes, but can be brought about by an invertible transformation whose existence and construction are determined by the nature of the instability of the dynamical system itself. After a brief review of this theory which also contains some relatively new remarks, we prove that classical Klein-Gordon field (both massive and massless) possess the structure of K-flow. This seems to provide the first examples of relativistic systems that are K-flows. Some of the implications of this result are briefly discussed. From a mathematical point of view, this seems to be a first step toward an ergodic theory of partial differential equations. In the process, we also provide an independant group-theoretic proof of the existence of incoming and outgoing subspaces of the scattering theory of Lax and Phillips for the wave equation.