First-principles energetics of water: a many-body analysis

Standard forms of density-functional theory (DFT) have good predictive power for many materials, but are not yet fully satisfactory for solid, liquid and cluster forms of water. We use a many-body separation of the total energy into its 1-body, 2-body (2B) and beyond-2-body (B2B) components to analyze the deficiencies of two popular DFT approximations. We show how machine-learning methods make this analysis possible for ice structures as well as for water clusters. We find that the crucial energy balance between compact and extended geometries can be distorted by 2B and B2B errors, and that both types of first-principles error are important.

Autonomous rigid body attitude synchronization

Control laws to synchronize attitudes in a swarm of fully actuated rigid bodies, in the absence of a common reference attitude or hierarchy in the swarm, are proposed in [Smith, T. R., Hanssmann, H., & Leonard, N.E. (2001). Orientation control of multiple underwater vehicles with symmetry-breaking potentials. In Proc. 40th IEEE conf. decision and control (pp. 4598-4603); Nair, S., Leonard, N. E. (2007). Stable synchronization of rigid body networks. Networks and Heterogeneous Media, 2(4), 595-624]. The present paper studies two separate extensions with the same energy shaping approach: (i) locally synchronizing the rigid bodies' attitudes, but without restricting their final motion and (ii) relaxing the communication topology from undirected, fixed and connected to directed, varying and uniformly connected. The specific strategies that must be developed for these extensions illustrate the limitations of attitude control with reduced information. © 2008 Elsevier Ltd.

Autonomous rigid body attitude synchronization

This paper studies some extensions to the decentralized attitude synchronization of identical rigid bodies. Considering fully actuated Euler equations, the communication links between the rigid bodies are limited and the available information is restricted to relative orientations and angular velocities. In particular, no leader nor external reference dictates the swarm's behavior. The control laws are derived using two classical approaches of nonlinear control - tracking and energy shaping. This leads to a comparison of two corresponding methods which are currently considered for distributed synchronization - consensus and stabilization of mechanical systems with symmetries. © 2007 IEEE.

First-principles energetics of water clusters and ice: a many-body analysis.

Standard forms of density-functional theory (DFT) have good predictive power for many materials, but are not yet fully satisfactory for cluster, solid, and liquid forms of water. Recent work has stressed the importance of DFT errors in describing dispersion, but we note that errors in other parts of the energy may also contribute. We obtain information about the nature of DFT errors by using a many-body separation of the total energy into its 1-body, 2-body, and beyond-2-body components to analyze the deficiencies of the popular PBE and BLYP approximations for the energetics of water clusters and ice structures. The errors of these approximations are computed by using accurate benchmark energies from the coupled-cluster technique of molecular quantum chemistry and from quantum Monte Carlo calculations. The systems studied are isomers of the water hexamer cluster, the crystal structures Ih, II, XV, and VIII of ice, and two clusters extracted from ice VIII. For the binding energies of these systems, we use the machine-learning technique of Gaussian Approximation Potentials to correct successively for 1-body and 2-body errors of the DFT approximations. We find that even after correction for these errors, substantial beyond-2-body errors remain. The characteristics of the 2-body and beyond-2-body errors of PBE are completely different from those of BLYP, but the errors of both approximations disfavor the close approach of non-hydrogen-bonded monomers. We note the possible relevance of our findings to the understanding of liquid water.

Reactive Many-Body Expansion for a Protonated Water Cluster.

We generalize the standard many-body expansion technique that is used to approximate the total energy of a molecular system to enable the treatment of chemical reactions by quantum chemical techniques. By considering all possible assignments of atoms to monomer units of the many-body expansion and associating suitable weights with each, we construct a potential energy surface that is a smooth function of the nuclear positions. We derive expressions for this reactive many-body expansion energy and describe an algorithm for its evaluation, which scales polynomially with system size, and therefore will make the method feasible for future condensed phase simulations. We demonstrate the accuracy and smoothness of the resulting potential energy surface on a molecular dynamics trajectory of the protonated water hexamer, using the Hartree-Fock method for the many-body term and Møller-Plesset theory for the low order terms of the many-body expansion.

Motor effort alters changes of mind in sensorimotor decision making.

After committing to an action, a decision-maker can change their mind to revise the action. Such changes of mind can even occur when the stream of information that led to the action is curtailed at movement onset. This is explained by the time delays in sensory processing and motor planning which lead to a component at the end of the sensory stream that can only be processed after initiation. Such post-initiation processing can explain the pattern of changes of mind by asserting an accumulation of additional evidence to a criterion level, termed change-of-mind bound. Here we test the hypothesis that physical effort associated with the movement required to change one's mind affects the level of the change-of-mind bound and the time for post-initiation deliberation. We varied the effort required to change from one choice target to another in a reaching movement by varying the geometry of the choice targets or by applying a force field between the targets. We show that there is a reduction in the frequency of change of mind when the separation of the choice targets would require a larger excursion of the hand from the initial to the opposite choice. The reduction is best explained by an increase in the evidence required for changes of mind and a reduced time period of integration after the initial decision. Thus the criteria to revise an initial choice is sensitive to energetic costs.

When is a symmetric body-hinge structure isostatic?

A symmetry-extended mobility rule is formulated for body-hinge frameworks and used to derive necessary symmetry conditions for isostatic (statically and kinematically indeterminate) frameworks. Constructions for symmetric body-hinge frameworks with an isostatic scalar count are reported, and symmetry counts are used to examine these structures for hidden, symmetry-detectable mechanisms. Frameworks of this type may serve as examples for exploration of a symmetry extension of the (now proven) 'molecular conjecture'. © 2014 Elsevier Ltd. All rights reserved.