Search results for "COMPUTATION"
showing 10 items of 7362 documents
Monte Carlo Simulations of Parallel Charged Platelets as an Approach to Tactoid Formation in Clay
2013
The free energy of interaction between parallel charged platelets with divalent counterions has been calculated using Monte Carlo simulations to investigate the electrostatic effects on aggregation. The platelets are primarily intended to represent clay particles. With divalent counterions, the free energy for two platelets or two tactoids (clusters of parallel platelets) shows a minimum at a short separation due to the attraction caused by ion-ion correlations. In a salt-free system, the free energy of interaction has a long-range repulsive tail beyond the minimum. The repulsion increases for tactoids with larger aggregation numbers, whereas the depth of the free-energy minimum is graduall…
Organocatalysts Fold to Generate an Active Site Pocket for the Mannich Reaction
2017
Catalysts containing urea, thiourea and tertiary amine groups fold into a three-dimensional organized structure in solution both in the absence as well as in the presence of substrates or substrate analogues, as indicated by solution NMR and computational studies. These foldamer catalysts promote Mannich reactions with both aliphatic and aromatic imines and malonate esters. Hammett plot and secondary kinetic isotope effects provide evidence for the C-C bond forming event as the turnoverlimiting step of the Mannich reaction. Computational studies suggest two viable pathways for the C-C bond formation step, differing in the activation modes of the malonate and imine substrates. The results sh…
Thriving Rough Sets: 10th Anniversary - Honoring Professor Zdzisław Pawlak's Life and Legacy & 35 Years of Rough Sets
2017
This special book is dedicated to the memory of Professor Zdzisław Pawlak, the father of rough set theory, in order to commemorate both the 10th anniversary of his passing and 35 years of rough set theory. The book consists of 20 chapters distributed into four sections, which focus in turn on a historical review of Professor Zdzisław Pawlak and rough set theory; a review of the theory of rough sets; the state of the art of rough set theory; and major developments in rough set based data mining approaches. Apart from Professor Pawlak’s contributions to rough set theory, other areas he was interested in are also included. Moreover, recent theoretical studies and advances in applications are a…
On Using Decision Maker Preferences with ParEGO
2017
In this paper, an interactive version of the ParEGO algorithm is introduced for identifying most preferred solutions for computationally expensive multiobjective optimization problems. It enables a decision maker to guide the search with her preferences and change them in case new insight is gained about the feasibility of the preferences. At each interaction, the decision maker is shown a subset of non-dominated solutions and she is assumed to provide her preferences in the form of preferred ranges for each objective. Internally, the algorithm samples reference points within the hyperbox defined by the preferred ranges in the objective space and uses a DACE model to approximate an achievem…
Pressure-Induced Deformation of Pillar-Type Profiled Membranes and Its Effects on Flow and Mass Transfer
2019
In electro-membrane processes, a pressure difference may arise between solutions flowing in alternate channels. This transmembrane pressure (TMP) causes a deformation of the membranes and of the fluid compartments. This, in turn, affects pressure losses and mass transfer rates with respect to undeformed conditions and may result in uneven flow rate and mass flux distributions. These phenomena were analyzed here for round pillar-type profiled membranes by integrated mechanical and fluid dynamics simulations. The analysis involved three steps: (1) A conservatively large value of TMP was imposed, and mechanical simulations were performed to identify the geometry with the minimum pillar density…
Can the absence of solvation of neutral reagents by ionic liquids be responsible for the high reactivity in base-assisted intramolecular nucleophilic…
2005
[reaction: see text] The kinetics of the rearrangement of the Z-phenylhydrazone of 3-benzoyl-5-phenyl-1,2,4-oxadiazole (1a) into the relevant 4-benzoylamino-2,5-diphenyl-1,2,3-triazole (2a) induced by amines have been studied in two room-temperature ionic liquids (IL-1, [BMIM][BF4] and IL-2, [BMIM][PF6]). The data collected show that the reaction occurs faster in ionic liquids than in other conventional solvents previously studied (both polar or apolar, protic or aprotic). Presumably, this could depend on their peculiar ability to minimize the strong substrate-solvent, amine-solvent and amine-amine interactions occurring in conventional solvents.
The Photocycle of Bacteriophytochrome Is Initiated by Counterclockwise Chromophore Isomerization.
2022
Photoactivation of bacteriophytochrome involves a cis–trans photoisomerization of a biliverdin chromophore, but neither the precise sequence of events nor the direction of the isomerization is known. Here, we used nonadiabatic molecular dynamics simulations on the photosensory protein dimer to resolve the isomerization mechanism in atomic detail. In our simulations the photoisomerization of the D ring occurs in the counterclockwise direction. On a subpicosecond time scale, the photoexcited chromophore adopts a short-lived intermediate with a highly twisted configuration stabilized by an extended hydrogen-bonding network. Within tens of picoseconds, these hydrogen bonds break, allowing the c…
On the local mode behaviour of the XH2/XD2 and XD/XH fragments with respect to the deuterated species of the near local mode XH3(C3v ) molecule
2009
International audience; Effect of isotopic substitution in the near local mode, XH3(C3v), molecules is considered. On that basis it is shown that the spectroscopic properties of deuterated and/or di-deuterated isotopic species of the XH3(C3v) molecule with the value of interbond angle close to π/2 are analogous to the spectroscopic properties of its separate fragments: of a three-atomic local mode 'molecule' XH2/XD2 and of a diatomic XD/XH 'molecule'. The phosphine molecule is considered as an illustration.
The impact of classes of innovators on Technology, Financial Fragility and Economic Growth
2011
In this paper, we study innovation processes and technological change in an agent-based model. By including a behavioral switching among heterogeneous innovative firms, which can endogenously change among three different classes (single innovators, collaborative innovators and imitators) on the base of their R&D expenditures, the model is able to replicate, via simulations, well known industrial dynamic and growth type stylized facts. Moreover, we focus the analysis on the impact of these three innovation categories on micro, meso and macro aggregates. We find that collaborative companies are those having the highest positive impact on the economic system. The model is then used to study th…
A strategic approach for the discounted Shapley values
2014
The family of discounted Shapley values is analyzed for cooperative games in coalitional form. We consider the bargaining protocol of the alternating random proposer introduced in Hart and Mas-Colell (Econometrica 64:357–380, 1996). We demonstrate that the discounted Shapley values arise as the expected payoffs associated with the bargaining equilibria when a time discount factor is considered. In a second model, we replace the time cost with the probability that the game ends without agreements. This model also implements these values in transferable utility games, moreover, the model implements the \(\alpha \)-consistent values in the nontransferable utility setting.