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The partitioning of the ternary systems n-pentane/n-heptane/(helium or argon) at ambient conditions is investigated using configurational-bias Monte Carlo simulations in the
Gibbs ensemble. The results demonstrate that this approach yields very precise partition constants and free energies of transfer.
Simulations are carried out to study the dependence of the n-pentane partitioning with respect to the carrier gas, the system size, and the overall solute concentrations. None of the
changes of variables, within the ranges used here, has a significant effect on the alkane partitioning. However, chemical
potentials calculated via Widom's ghost particle insertions show a strong number dependence for phases containing relatively
few molecules of a given type. This problem originates from the fact that the chemical potential is calculated for a concentration
of real particles plus one ghost particle that is systematically larger than the equilibrium concentration. A simple correction
term is suggested to account for this problem.
Received: 13 May 1998 / Accepted: 18 June 1998 / Published online: 4 September 1998 相似文献
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Structure, stability, and electronic and NMR properties of [(Salen)Mn(III)](+)-derived intermediates/reactants in the epoxidation/amination of unfunctionalized olefins, namely [(Salen)Mn(V)O](+) (1-oxo), [(Salen)Mn(IV)O] (2-oxo), and [(Salen)Mn(V)N] (3), have been studied with the B3LYP density functional method. It has been shown that the (1)A, (3)A, and (5)A states of cationic 1-oxo species are virtually degenerate, while for the neutral 2-oxo species the ground (4)A state lies 6.4 kcal/mol lower than (2)A. In the nitrido species 3, the (1)A state has been shown to be the ground state in agreement with experiment. We have investigated isomerization of 1-oxo and 2-oxo species into unusual [(OSalen)Mn(III)](+) (1-N-oxo and 1-peroxo) and [(OSalen)Mn(II)] (2-N-oxo and 2-peroxo) species, respectively. For cationic species 1, the 1-N-oxo isomers are more stable (by 10-12 kcal/mol) than the 1-oxo isomer and are separated from the latter by 21-22 kcal/mol barriers. On the other hand, 1-peroxo isomers are calculated to be 14-16 kcal/mol higher than the 1-oxo isomer. For neutral species 2, however, both 2-N-oxo and 2-peroxo isomers lie significantly higher in energy than the 2-oxo isomer. It has been shown that coordination of axial imidazole ligand alters relative energies of spin states for 1- and 2-oxo species, destabilizing low-spin states. For singlet states of H(2)Salen, 1-oxo, and 3, we have calculated (1)H, (13)C, (15)N, and (17)O NMR chemical shifts using the gauge-independent-atomic orbital (GIAO) approach. 相似文献
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Gibbs ensemble Monte Carlo simulations were used to calculate the vapor-liquid and vapor-solid coexistence curves for benzene using two simple united-atom models. An extension of the Gibbs ensemble method that makes use of an elongated box containing a slab of the condensed phase with a vapor phase along one axis was employed for the simulations of the vapor-solid equilibria and the vapor-liquid equilibria at very low reduced temperatures. Configurational-bias and aggregation-volume-bias Monte Carlo techniques were applied to improve the sampling of particle transfers between the two simulation boxes and between the vapor and condensed-phase regions of the elongated box. An isotropic united-atom representation with six Lennard-Jones sites at the positions of the carbon atoms was used for both force fields, but one model contained three additional out-of-plane partial charge sites to explicitly represent benzene's quadrupolar interactions. Both models were fitted to reproduce the critical temperature and density of benzene and yield a fair representation of the vapor-liquid coexistence curve. In contrast, differences between the models are very large for the vapor-solid coexistence curve. In particular, the lack of explicit quadrupolar interactions for the 6-site model greatly reduces the energetic differences between liquid and solid phases, and this model yields a triple point temperature that is about a factor of 2 too low. In contrast, the 9-site model predicts a triple point of benzene at T = 253 +/- 6 K and p = 2.3 +/- 0.8 kPa in satisfactory agreement with the experimental data (T = 278.7 K and p = 4.785 kPa). 相似文献
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Dr. Christianus M. A. Leenders Gijs Jansen Martijn M. M. Frissen René P. M. Lafleur Dr. Ilja K. Voets Dr. Anja R. A. Palmans Prof. Dr. E. W. Meijer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(13):4608-4615
We introduce monosaccharides as versatile water‐soluble units to compatibilise supramolecular polymers based on the benzene‐1,3,5‐tricarboxamide (BTA) moiety with water. A library of monosaccharide‐based BTAs is evaluated, varying the length of the alkyl chain (hexyl, octyl, decyl and dodecyl) separating the BTA and saccharide units, as well as the saccharide units (α‐glucose, β‐glucose, α‐mannose and α‐galactose). In all cases, the monosaccharides impart excellent water compatibility. The length of the alkyl chain is the determining factor to obtain either long, one‐dimensional supramolecular polymers (dodecyl spacer), small aggregates (decyl spacer) or molecularly dissolved (octyl and hexyl) BTAs in water. For the BTAs comprising a dodecyl spacer, our results suggest that a cooperative self‐assembly process is operative and that the introduction of different monosaccharides does not significantly change the self‐ assembly behaviour. Finally, we investigate the potential of post‐assembly functionalisation of the formed supramolecular polymers by taking advantage of dynamic covalent bond formation between the monosaccharides and benzoxaboroles. We observe that the supramolecular polymers readily react with a fluorescent benzoxaborole derivative permitting imaging of these dynamic complexes by confocal fluorescence microscopy. 相似文献
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Katsunari Enomoto Pavle Djuricanin Ilja Gerhardt Omid Nourbakhsh Yoshiki Moriwaki Walter Hardy Takamasa Momose 《Applied physics. B, Lasers and optics》2012,109(1):149-157
We propose the use of superconducting microwave cavities for the focusing and deceleration of cold polar molecular beams. A superconducting cavity with a high quality factor produces a large ac Stark shift in polar molecules, which allow us to efficiently control molecular motion. Our discussion is based on the experimental characterization of a prototype cavity: a lead–tin-coated cylindrical copper cavity, which has a quality factor of 106 and tolerates several watts of input power. Such a microwave device provides a powerful way to control molecules not only in low-field-seeking states, but also in high-field-seeking states such as the ground rotational state. 相似文献
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Peckermann I Raabe G Spaniol TP Okuda J 《Chemical communications (Cambridge, England)》2011,47(17):5061-5063
Allyl and 2-methylallyl indium compounds were prepared by salt metathesis starting from indium trichloride and a Grignard reagent. They are highly fluxional in solution and reveal coordination numbers of the indium atoms of four and five in the solid state. 相似文献
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Andreeva DV Ip B Gurinov AA Tolstoy PM Denisov GS Shenderovich IG Limbach HH 《The journal of physical chemistry. A》2006,110(37):10872-10879
The ability of strongly sterically hindered pyridines to form hydrogen bonded complexes was inspected using low-temperature 1H and 15N NMR spectroscopy in a liquefied Freon mixture. The proton acceptors were 2,6-di(tert-butyl)-4-methyl- and 2,6-di(tert-butyl)-4-diethylaminopyridine; the proton donors were hydrogen tetrafluoroborate, hydrogen chloride, and hydrogen fluoride. The presence of the tert-butyl groups in the ortho positions dramatically perturbed the geometry of the forming hydrogen bonds. As revealed by experiment, the studied crowded pyridines could form hydrogen bonded complexes with proton donors exclusively through their protonation. Even the strongest small proton acceptor, anion F-, could not be received by the protonated base. Instead, the simplest hydrogen bonded complex involved the [FHF]- anion. This complex was characterized by the shortest possible N...F distance of about 2.8 A. Because the ortho tert-butyl groups did not prevent the hydrogen bond interaction between the protonated center and the anion completely, an increase of the pyridine basicity caused a further shortening of the N-H distance and a weakening of the hydrogen bond to the counterion. 相似文献
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Zhenzhen Yang Hao Chen Bo Li Wei Guo Kecheng Jie Yifan Sun De‐en Jiang Ilja Popovs Sheng Dai 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(39):13901-13905
Progress toward the preparation of porous organic polymers (POPs) with task‐specific functionalities has been exceedingly slow—especially where polymers containing low‐oxidation phosphorus in the structure are concerned. A two‐step topotactic pathway for the preparation of phosphabenzene‐based POPs (Phos‐POPs) under metal‐free conditions is reported, without the use of unstable phosphorus‐based monomers. The synthetic route allows additional functionalities to be introduced into the porous polymer framework with ease. As an example, partially fluorinated Phos‐POPs (F‐Phos‐POPs) were obtained with a surface area of up to 591 m2 g?1. After coordination with Ru species, a Ru/F‐Phos‐POPs catalyst exhibited high catalytic efficiency in the formylation of amines (turnover frequency up to 204 h?1) using a CO2/H2 mixture, in comparison with the non‐fluorinated analogue (43 h?1) and a Au/TiO2 heterogeneous catalysts reported previously (<44 h?1). This work describes a practical method for synthesis of porous organic phosphorus‐based polymers with applications in transition‐metal‐based heterogeneous catalysis. 相似文献