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111.
A challenge in free energy calculation for complex molecular systems by computer simulation is to obtain a reliable estimate within feasible computational time. In this study, we suggest an answer to this challenge by exploring a simple method, overlap sampling (OS), for producing reliable free-energy results in an efficient way. The formalism of the OS method is based on ensuring sampling of important overlapping phase space during perturbation calculations. This technique samples both forward and reverse free energy perturbation (FEP) to improve the free-energy calculation. It considers the asymmetry of the FEP calculation and features an ability to optimize both the precision and the accuracy of the measurement without affecting the simulation process itself. The OS method is tested at two optimization levels: no optimization (simple OS), and full optimization (equivalent to Bennett's method), and compared to conventional FEP techniques, including the widely used direct FEP averaging method, on three alchemical mutation systems: (a) an anion transformation in water solution, (b) mutation between methanol and ethane, and (c) alchemical change of an adenosine molecule. It is consistently shown that the reliability of free-energy estimates can be greatly improved using the OS techniques at both optimization levels, while the performance of Bennett's method is particularly striking. In addition, the efficiency of a calculation can be significantly improved because the method is able to (a) converge to the right answer quickly, and (b) work for large perturbations. The basic two-stage OS method can be extended to admit additional stages, if needed. We suggest that the OS method can be used as a general perturbation technique for computing free energy differences in molecular simulations. 相似文献
112.
113.
X. Bokhimi A. Morales E. Ortíz T. López R. Gómez J. Navarrete 《Journal of Sol-Gel Science and Technology》2004,29(1):31-40
Sol-gel titania was sulfated by using sulfuric acid as hydrolysis catalyst, or by impregnating with ammonium sulfate fresh samples prepared with nitric acid or ammonium hydroxide as hydrolysis catalyst. Samples were characterized with X-ray powder diffraction, infrared spectroscopy, thermogravimetry and atomic absorption spectroscopy. Sulfate ions were found anchored to brookite and anatase phases, because they have short O—O atomic bond lengths slightly larger than the largest O—O bond length of sulfate ion. Since the shortest O—O atomic bond in anatase is smaller than the one in brookite, the sulfate ions are then less deformed when they are anchored to anatase, and consequently more stable. Therefore when the sample temperature is raised, the brookite with sulfate ions was transformed mainly to anatase and not into rutile, which is the most probably transformation when these ions are not involved. Sulfate ions also hindered anatase and brookite crystallite growing and stabilized the crystalline structure of anatase. When the sulfate ions are lost the crystalline anatase phase is transformed into rutile, leaving a large number of vacancies that favored atom diffusion and consequently the growing of rutile crystallites. The crystalline evolution of the samples as a function of the annealing temperature is almost independent of the sulfating method. 相似文献
114.
115.
Yuichi Michiue 《Journal of solid state chemistry》2006,179(8):2578-2583
Phase relations of rutile, freudenbergite, and hollandite structures were examined in the pseudobinary system NaCrO2-TiO2 (i.e., NaxCrxTi8−xO16) at 1350 °C. The hollandite structure was obtained in the composition range 1.7?x?2.0. The symmetry of the samples at room temperature was tetragonal for x=1.7 and 1.75, and monoclinic for x=1.8 and above. Single crystals of monoclinic hollandite Na2Cr2Ti6O16 were grown and the structure refinement has been carried out using an X-ray diffraction technique. The space group was I2/m and cell parameters were a=10.2385(11), b=2.9559(9), c=9.9097(11)Å, and β=90.545(9)° with Z=1. The Na ion distribution in the tunnel was markedly deformed from that in the tetragonal form. It was suggested that Cr/Ti ratios were different between the two framework metal sites. 相似文献
116.
Jungui DaiShujun Zhang Jun-ichi SakaiJiao Bai Yoshiki OkuMasayoshi Ando 《Tetrahedron letters》2003,44(5):1091-1094
Three C-14 oxygenated taxanes, 2α,5α,10β,14β-tetraacetoxytaxa-4(20),11-diene (1), 2α,5α,10β-triacetoxy-14β-(2-methylbutyryloxy)taxa-4(20),11-diene (2), and yunanaxane (3), major products of callus cultures of Taxus spp., were regio- and stereoselectively hydroxylated at the 7β position by a fungus, Absidia coerulea IFO 4011. Intriguingly, when 1 was co-administered with β-cyclodextrin and incubated with the fungus cell cultures, three other compounds 5α,9α,10β,13α-tetraacetoxytaxa-4(20),11-dien-14β-ol (7), 5α,9α,10β,13α-tetraacetoxytaxa-4(20),11-dien-1β-ol (8) and 5α,9α,10β,13α-tetraacetoxy-11(15→1) abeotaxa-4(20),11-dien-15-ol (9) were obtained. 相似文献
117.
Ramendra Pratap 《Tetrahedron letters》2007,48(36):6318-6320
An easy and efficient synthesis of phenanthrene derivatives through base catalyzed ring transformation of 4-sec-amino-2-oxo-5,6-dihydro-2H-benzo[h]chromene-3-carbonitriles with acetyltrimethylsilane is described in good yields. The advantage of this reaction is the direct transformation of 2-oxobenzo[h]chromene into phenanthrene via C-C insertion from acetyltrimethylsilane. 相似文献
118.
Titanate nanoribbons were prepared via a hydrothermal treatment of rutile-type TiO2 powders in a 10 M NaOH solution at 200 °C for 48 h. The as-prepared titanate nanoribbons were then hydrothermally post-treated at 150 °C for 12-36 h. The titanate nanoribbons before and after hydrothermal post-treatment were characterized with FESEM, XRD, TEM, UV-VIS and nitrogen adsorption-desorption isotherms. The results showed that the hydrothermal post-treatment not only promoted the phase transformation from titanate to anatase TiO2, but also was beneficial to the removal of Na+ ions remained in the titanate nanoribbons. After hydrothermal post-treatment, the TiO2 samples retained the one-dimensional structure feature of the titanate nanoribbons and showed an obvious increase in the specific surface area and the pore volume. 相似文献
119.
A. Miele B. P. Mohanty P. Venkataraman Y. M. Kuo 《Journal of Optimization Theory and Applications》1982,38(1):97-109
This paper contains general transformation techniques useful to convert minimax problems of optimal control into the Mayer-Bolza problem of the calculus of variations [Problem (P)]. We consider two types of minimax problems: minimax problems of Type (Q), in which the minimax function depends on the state and does not depend on the control; and minimax problems of Type (R), in which the minimax function depends on both the state and the control. Both Problem (Q) and Problem (R) can be reduced to Problem (P).For Problem (Q), we exploit the analogy with a bounded-state problem in combination with a transformation of the Jacobson type. This requires the proper augmentation of the state vectorx(t), the control vectoru(t), and the parameter vector , as well as the proper augmentation of the constraining relations. As a result of the transformation, the unknown minimax value of the performance index becomes a component of the parameter vector being optimized.For Problem (R), we exploit the analogy with a bounded-control problem in combination with a transformation of the Valentine type. This requires the proper augmentation of the control vectoru(t) and the parameter vector , as well as the proper augmentation of the constraining relations. As a result of the transformation, the unknown minimax value of the performance index becomes a component of the parameter vector being optimized.In a subsequent paper (Part 2), the transformation techniques presented here are employed in conjunction with the sequential gradient-restoration algorithm for solving optimal control problems on a digital computer; both the single-subarc approach and the multiple-subarc approach are discussed.This research was supported by the National Science Foundation, Grant No. ENG-79-18667, and by Wright-Patterson Air Force Base, Contract No. F33615-80-C3000. This paper is a condensation of the investigations reported in Refs. 1–7. The authors are indebted to E. M. Coker and E. M. Sims for analytical and computational assistance. 相似文献
120.
J. Vzquez D. García-G. Barreda P.L. Lpez-Alemany P. Villares R. Jimnez-Garay 《Thermochimica Acta》2005,430(1-2):173-182
A method has been developed for analysing the evolution with time of the volume fraction transformed and for calculating the kinetic parameters at non-isothermal reactions in materials involving formation and growth of nuclei. By considering the assumptions of extended volume and random nucleation, a general expression of the fraction transformed as a function of time has been obtained in isothermal crystallization processes. Considering the mutual interference of regions growing from separate nuclei the Johnson–Mehl–Avrami equation has been deduced as a particular case. The application of the transformation rate equation to the non-isothermal processes has been carried out under the restriction of a nucleation which takes place early in the transformation and the nucleation frequency is zero thereafter. Under these conditions, the kinetic parameters have been deduced by using the techniques of data analysis of single-scan and multiple-scan. The theoretical method developed has been applied to the glass-crystal transformation kinetics of the semiconducting Ge0.13Sb0.23Se0.64 alloy. The kinetic parameters obtained according to both techniques differ by only about 2.5%, which confirms the reliability and accuracy of the single-scan technique when calculating the above-mentioned parameters in non-isothermal transformation processes. The phases at which the above-mentioned semiconducting glass crystallizes after the thermal process have been identified by X-ray diffraction. The diffractogram of the transformed material shows that microcrystallites of Sb2Se3 and GeSe are associated with the crystallization process, remaining a residual amorphous matrix. 相似文献