Evaluation of B3LYP, X3LYP, and M06-class density functionals for predicting the binding energies of neutral, protonated, and deprotonated water clusters

In this paper we assess the accuracy of the B3LYP, X3LYP, and newly developed M06-L, M06-2X, and M06 functionals to predict the binding energies of neutral and charged water clusters including (H_2O)_n, n = 2−8, 20), H_3O+(H_2O_)n, n = 1−6, and OH−(H_2O)_n, n = 1−6. We also compare the predicted energies of two ion hydration and neutralization reactions on the basis of the calculated binding energies. In all cases, we use as benchmarks calculated binding energies of water clusters extrapolated to the complete basis set limit of the second-order Møller−Plesset perturbation theory with the effects of higher order correlation estimated at the coupled-cluster theory with single, double, and perturbative triple excitations in the aug-cc-pVDZ basis set. We rank the accuracy of the functionals on the basis of the mean unsigned error (MUE) between calculated benchmark and density functional theory energies. The corresponding MUE (kcal/mol) for each functional is listed in parentheses. We find that M06-L (0.73) and M06 (0.84) give the most accurate binding energies using very extended basis sets such as aug-cc-pV5Z. For more affordable basis sets, the best methods for predicting the binding energies of water clusters are M06-L/aug-cc-pVTZ (1.24), B3LYP/6-311++G(2d,2p) (1.29), and M06/aug-cc-PVTZ (1.33). M06-L/aug-cc-pVTZ also gives more accurate energies for the neutralization reactions (1.38), whereas B3LYP/6-311++G(2d,2p) gives more accurate energies for the ion hydration reactions (1.69)

Shock Induced Decomposition and Sensitivity of Energetic Materials by ReaxFF Molecular Dynamics

We develop strain-driven compression-expansion technique using molecular dynamics (MD) with reactive force fields (ReaxFF) to study the impact sensitivity of energetic materials. It has been applied to simulation of 1,3,5-trinitrohexahydro-s-triazine (RDX) crystal subjected to high-rate compression typical at the detonation front. The obtained results show that at lower compression ratio x = 1-V/V040%) all molecules decompose very quickly. We have observed both primary and secondary reactions during the decomposition process as well as production of various intermediates (NO2, NO, HONO, OH) and final products (H2O, N2, CO, CO2). The results of strain-driven compression-expansion modeling are in a good agreement with previous ReaxFF-MD shock simulations in RDX. Proposed approach might be useful for a quick test of sensitivity of energetic materials under conditions of high strain rate loading

Thermal properties of fluorinated graphene

Large scale atomistic simulations using the reactive force field approach (ReaxFF) are implemented to investigate the thermomechanical properties of fluorinated graphene (FG). A new set of parameters for the reactive force field potential (ReaxFF) optimized to reproduce key quantum mechanical properties of relevant carbon-fluor cluster systems are presented. Molecular dynamics (MD) simulations are used to investigate the thermal rippling behavior of FG and its mechanical properties and compare them with graphene (GE), graphane (GA) and a sheet of BN. The mean square value of the height fluctuations $$ and the height-height correlation function $H(q)$ for different system sizes and temperatures show that FG is an un-rippled system in contrast to the thermal rippling behavior of graphene (GE). The effective Young's modulus of a flake of fluorinated graphene is obtained to be 273 N/m and 250 N/m for a flake of FG under uniaxial strain along arm-chair and zig-zag direction, respectively.Comment: To appear in Phys. Rev.

Mechanical Properties and Fracture Dynamics of Silicene Membranes

As graphene became one of the most important materials today, there is a renewed interest on others similar structures. One example is silicene, the silicon analogue of graphene. It share some the remarkable graphene properties, such as the Dirac cone, but presents some distinct ones, such as a pronounced structural buckling. We have investigated, through density functional based tight-binding (DFTB), as well as reactive molecular dynamics (using ReaxFF), the mechanical properties of suspended single-layer silicene. We calculated the elastic constants, analyzed the fracture patterns and edge reconstructions. We also addressed the stress distributions, unbuckling mechanisms and the fracture dependence on the temperature. We analysed the differences due to distinct edge morphologies, namely zigzag and armchair

Development and Validation of a ReaxFF Reactive Force Field for Cu Cation/Water Interactions and Copper Metal/Metal Oxide/Metal Hydroxide Condensed Phases

To enable large-scale reactive dynamic simulations of copper oxide/water and copper ion/water interactions we have extended the ReaxFF reactive force field framework to Cu/O/H interactions. To this end, we employed a multistage force field development strategy, where the initial training set (containing metal/metal oxide/metal hydroxide condensed phase data and [Cu(H_2O)_n]^(2+) cluster structures and energies) is augmented by single-point quantum mechanices (QM) energies from [Cu(H_2O)_n]^(2+) clusters abstracted from a ReaxFF molecular dynamics simulation. This provides a convenient strategy to both enrich the training set and to validate the final force field. To further validate the force field description we performed molecular dynamics simulations on Cu^(2+)/water systems. We found good agreement between our results and earlier experimental and QM-based molecular dynamics work for the average Cu/water coordination, Jahn−Teller distortion, and inversion in [Cu(H_2O)_6]^(2+) clusters and first- and second-shell O−Cu−O angular distributions, indicating that this force field gives a satisfactory description of the Cu-cation/water interactions. We believe that this force field provides a computationally convenient method for studying the solution and surface chemistry of metal cations and metal oxides and, as such, has applications for studying protein/metal cation complexes, pH-dependent crystal growth/dissolution, and surface catalysis

ARQUEOLOGIA ENGAJADA: MAPEAMENTO PARTICIPATÓ- RIO COM OS POVOS INDÍGENAS DA BACIA DO ALTO RIO MARONI, NORTE DA AMAZÔNIA

New perspectives on the sociopolitical landscapes of past tropical forest cultures have emerged the past twenty years in Amazonian archaeology.Evolving relationships between archaeologists and indigenous Amazonian people, as well as integrating archaeological practice with indigenousAmazonian knowledge, has recently led to groundbreaking scientific discoveries in Amazonia. The present article is a discussion on an ongoing participatory mapping project highlighting this emerging tradition of archaeologists engaging with indigenous people. Specifically, thisparticipatory mapping project in the Eastern Guiana Highlands (Suriname, French Guiana, and Brazil), is part of a recent process of sharing the research agendas of both an anthropologist/archaeologist and the indigenous Amazonian people. Throughout this article, the challenging potential of interdisciplinary and multi-scalar research on historically situated sociopolitical processes is foregrounded. Nevertheless, this emergent relationship between indigenous Amazonian people and a growing number of archaeologists is in its initial stages.Keywords: Indigenous archaeologies, historical archaeology, participatory mappingNovas perspectivas sobre as paisagens sociopolíticas de culturas de florestas tropicais do passado têm surgido nos últimos vinte anos na arqueologia amazônica. A evolução das relações entre arqueólogos e povos indígenas da Amazônia, bem como a integração da prática arqueológica com o conhecimento dos povos indígenas da região, levou recentemente a descobertas científicas surpreendentes na Amazônia. O presente artigo é um relato de pesquisa sobre um projeto de mapeamento participativo em curso, destacando a tradição emergente de arqueólogos que se envolvem com os povos indígenas. Especificamente, este projeto de mapeamento participativo é parte de um processo recente de compartilhamento das agendas de pesquisa de antropólogo/arqueólogo e os povos indígenas amazônicos das terras altas das Guianas (Suriname, Guiana Francesa e Brasil). Ao longo deste artigo, o desafiador potencial de pesquisa interdisciplinar e de multi-escala em processos sociopolíticos historicamente situados está em primeiro plano. No entanto, esta relação emergente entre povos indígenas amazônicos e um crescente número de arqueólogos envolvidos está em estágios iniciais. Palavras-chave: Arqueologias indígenas, arqueologia histórica, mapeamento participativo

Pilot, Rollout and Monte Carlo Tree Search Methods for Job Shop Scheduling

Greedy heuristics may be attuned by looking ahead for each possible choice, in an approach called the rollout or Pilot method. These methods may be seen as meta-heuristics that can enhance (any) heuristic solution, by repetitively modifying a master solution: similarly to what is done in game tree search, better choices are identified using lookahead, based on solutions obtained by repeatedly using a greedy heuristic. This paper first illustrates how the Pilot method improves upon some simple well known dispatch heuristics for the job-shop scheduling problem. The Pilot method is then shown to be a special case of the more recent Monte Carlo Tree Search (MCTS) methods: Unlike the Pilot method, MCTS methods use random completion of partial solutions to identify promising branches of the tree. The Pilot method and a simple version of MCTS, using the $\varepsilon$-greedy exploration paradigms, are then compared within the same framework, consisting of 300 scheduling problems of varying sizes with fixed-budget of rollouts. Results demonstrate that MCTS reaches better or same results as the Pilot methods in this context.Comment: Learning and Intelligent OptimizatioN (LION'6) 7219 (2012