Symmetric and asymmetric triple excitation corrections for the orbital-optimized coupled-cluster doubles method: improving upon CCSD(T) and CCSD(T)(Λ): preliminary application

Symmetric and asymmetric triple excitation corrections for the orbital-optimized coupled-cluster doubles (OO-CCD or simply "OD" for short) method are investigated. The conventional symmetric and asymmetric perturbative triples corrections [(T) and (T)(Λ)] are implemented, the latter one for the first time. Additionally, two new triples corrections, denoted as OD(Λ) and OD(Λ)(T), are introduced. We applied the new methods to potential energy surfaces of the BH, HF, C(2), N(2), and CH(4) molecules, and compare the errors in total energies, with respect to full configuration interaction, with those from the standard coupled-cluster singles and doubles (CCSD), with perturbative triples [CCSD(T)], and asymmetric triples correction (CCSD(T)(Λ)) methods. The CCSD(T) method fails badly at stretched geometries, the corresponding nonparallelity error is 7-281 kcal mol(-1), although it gives reliable results near equilibrium geometries. The new symmetric triples correction, CCSD(Λ), noticeably improves upon CCSD(T) (by 4-14 kcal mol(-1)) for BH, HF, and CH(4); however, its performance is worse than CCSD(T) (by 1.6-4.2 kcal mol(-1)) for C(2) and N(2). The asymmetric triples corrections, CCSD(T)(Λ) and CCSD(Λ)(T), perform remarkably better than CCSD(T) (by 5-18 kcal mol(-1)) for the BH, HF, and CH(4) molecules, while for C(2) and N(2) their results are similar to those of CCSD(T). Although the performance of CCSD and OD is similar, the situation is significantly different in the case of triples corrections, especially at stretched geometries. The OD(T) method improves upon CCSD(T) by 1-279 kcal mol(-1). The new symmetric triples correction, OD(Λ), enhances the OD(T) results (by 0.01-2.0 kcal mol(-1)) for BH, HF, and CH(4); however, its performance is worse than OD(T) (by 1.9-2.3 kcal mol(-1)) for C(2) and N(2). The asymmetric triples corrections, OD(T)(Λ) and OD(Λ)(T), perform better than OD(T) (by 2.0-6.2 kcal mol(-1)). The latter method is slightly better for the BH, HF, and CH(4) molecules. However, for C(2) and N(2) the new results are similar to those of OD(T). For the BH, HF, and CH(4) molecules, OD(Λ)(T) provides the best potential energy curves among the considered methods, while for C(2) and N(2) the OD(T) method prevails. Hence, for single-bond breaking the OD(Λ)(T) method appears to be superior, whereas for multiple-bond breaking the OD(T) method is better.     

Problems in Chemistry

利用数学方法解决化学问题是化学及相关专业学生必备的技能之一。作者Daley,H.O.针对这一需要,为大学学习普通化学的学生编写了这本习题集。通过解题学生可以检验自己对化学原理掌握的深浅程度。     

News in Brief

About 200 billion yuan (24.3 billion US dollars) of investment was spent in infrastructure projects in west China region in 2003, occupying 55.2 percent of the country's total annual investment to the region. According to a leading group conducting the west development strategy, China plans to invest 363.5 billion yuan (44 billion US dollars) to the west in 2003, including 76 key projects.     

St?rkebestimmung in technischen Produkten und in Pflanzenteilen

Ohne Zusammenfassung     

L?slichkeit der arsensauren Ammon-Magnesia in reinem, in Ammoniak enthaltendem, in Salmiak enthaltendem und in Salmiak und Ammoniak enthaltendem Wasser

Ohne Zusammenfassung     

Die Schwefels?ure in Ledern und in sulfierten Extrakten

Ohne Zusammenfassung     

Evidence for dose rate effect in gamma-radiolysis—II. Methylmethoxyacetate in 2,3-dimethylbutane and in cyclohexane

Solutions of 2,3-dimethylbutane (DMB) and cyclohexane containing a captodative solute, methylmethoxyacetate (MMA), were irradiated (continuous wave). Alkane dimeric products were analysed by capillary gas chromatography. G-yields were estimated as a function of the concentration of the captodative solute. By reaction with alkyl radicals, the captodative solute gives the free radical stabilized by the captodative effect. Combination reaction of this radical with itself or with alkyl radicals gives solute or mixed dimer which were also analysed. A large intensity effect was noticed, as was seen in the solutions of n-hexane-MMA. Dose effect was definitely rejected.     

Die Polarographie von Blei in Hydroxyd- und in Cyanidl?sung

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Antioxidant activity of β-carotene compounds in different in vitro assays

β-Carotene (BC) is the most abundant carotenoid in human diet, almost solely as(all-E)-isomer. Significant amounts of (Z)-isomers of BC are present in processed food as well as in mammalian tissues. Differences are described for the activity of various BC isomers in forming retinal and protecting against cancer and cardiovascular diseases. Eccentric cleavage of BC leads to degradation products such as carotenals. A variety of negative consequences were published for the non-vitamin A active BC metabolites, such as inducing the carcinogenesis of benzo[a]pyrene, impairing mitochondrial function, or increasing CYP activity. To increase the knowledge on the antioxidant activity, a variety of BC isomers and metabolites were tested in various in vitro assays. In the present study, no ferric reducing activity (FRAP assay) was observed for the BC isomers. Between the major BC isomers (all-E, 9Z, and 13Z) no significant differences in bleaching the ABTS●+ (αTEAC assay) or in scavenging peroxyl radicals (ROO●) generated by thermal degradation of AAPH (using a chemiluminescence assay) were detected.However, the (15Z)-isomer was less active, maybe due to its low stability. The degradation to β-apo-carotenoids increased FRAP activity and ROO● scavenging activity compared to the parent molecule. Dependence on chain length and character of the terminal function was determined in αTEAC assay with following order of increasing activity: β-apo-8'-carotenal < β-apo-8'-carotenoic acid ethyl ester < 6'-methyl-β-apo-6'-carotene-6'-one (citranaxanthin). The results indicate that BC does not lose its antioxidant activity by degradation to long chain breakdown products.     

Zur Schnellbestimmung von Wasser in Teig und in Geb?ck

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C-C activation in the solid state in an organometallic σ-complex

Herein is reported the synthesis, by a solid-state reaction from [Ir(NBD)(2)(P(i)Pr(3))][BAr(F)(4)], of the first example of a C-C σ-complex with iridium, [Ir(BINOR-S)(P(i)Pr(3))][BAr(F)(4)]. This compound is unique in that in the solid state it undergoes reversible activation of the C-C single bond that interacts with the metal center, establishing a temperature-dependent equilibrium between Ir(III) C-C σ/Ir(V) bis-alkyl complexes. This process has been interrogated by variable-temperature X-ray diffraction, NMR spectroscopy, and DFT calculations.     

Intermediate Filaments in Higher Plant Cells and Their Reconstitution in vitro

Delicate networks of 10-nm filaments were found to exist widely in suspension cells of cultured carrot and root tip cells of pea by selective extraction combined with whole mount and diethylene glycol distearate plastic embedment-free section for electron microscopy. These filament components are polypeptides of 52, 58, 62—64 and 50kD using Western blot analysis. A relatively uniform 10-nm filaments, as well as bundle of such filaments could be reconstituted in vitro. The reconstituted filaments were indistinguishable from native plant intermediate filaments in morphology and protein components. Thus the intermediate filaments are actually present in cytoplasm of higher plants. We also found no obvious specificity in tissues and species by comparison of the proteins among various types of plant cells.     

Die Kohlenstoffbestimmung in Chloroestern der Orthokiesels?ure und in Alkylchlorsilanen

Ohne Zusammenfassung     

Development of X-ray fluorescence analysis in Russia in 1991–2010

A review attempted to examine the results of studies in X-ray fluorescence (XRF) analysis performed by Russian authors for the period from 1991 to the present time is given. This proved to be quite a challenge, since the number of articles published only on the theory and practice of XRF (excluding the development of equipment) exceeded 500. Therefore, the author had to limit himself to a more detailed presentation of only several important achievements. Further information, if necessary, can be found in the cited reviews.