Near-infrared photoabsorption by C(60) dianions in a storage ring

We present a detailed study of the electronic structure and the stability of C(60) dianions in the gas phase. Monoanions were extracted from a plasma source and converted to dianions by electron transfer in a Na vapor cell. The dianions were then stored in an electrostatic ring, and their near-infrared absorption spectrum was measured by observation of laser induced electron detachment. From the time dependence of the detachment after photon absorption, we conclude that the reaction has contributions from both direct electron tunneling to the continuum and vibrationally assisted tunneling after internal conversion. This implies that the height of the Coulomb barrier confining the attached electrons is at least similar to 1.5 eV. For C(60)(2-) ions in solution electron spin resonance measurements have indicated a singlet ground state, and from the similarity of the absorption spectra we conclude that also the ground state of isolated C(60)(2-) ions is singlet. The observed spectrum corresponds to an electronic transition from a t(1u) lowest unoccupied molecular orbital (LUMO) of C(60) to the t(1g) LUMO+1 level. The electronic levels of the dianion are split due to Jahn-Teller coupling to quadrupole deformations of the molecule, and a main absorption band at 10723 cm(-1) corresponds to a transition between the Jahn-Teller ground states. Also transitions from pseudorotational states with 200 cm(-1) and (probably) 420 cm(-1) excitation are observed. We argue that a very broad absorption band from about 11 500 cm(-1) to 13 500 cm(-1) consists of transitions to so-called cone states, which are Jahn-Teller states on a higher potential-energy surface, stabilized by a pseudorotational angular momentum barrier. A previously observed, high-lying absorption band for C(60)(-) may also be a transition to a cone state

Service composition in stochastic settings

With the growth of the Internet-of-Things and online Web services, more services with more capabilities are available to us. The ability to generate new, more useful services from existing ones has been the focus of much research for over a decade. The goal is, given a specification of the behavior of the target service, to build a controller, known as an orchestrator, that uses existing services to satisfy the requirements of the target service. The model of services and requirements used in most work is that of a finite state machine. This implies that the specification can either be satisfied or not, with no middle ground. This is a major drawback, since often an exact solution cannot be obtained. In this paper we study a simple stochastic model for service composition: we annotate the tar- get service with probabilities describing the likelihood of requesting each action in a state, and rewards for being able to execute actions. We show how to solve the resulting problem by solving a certain Markov Decision Process (MDP) derived from the service and requirement specifications. The solution to this MDP induces an orchestrator that coincides with the exact solution if a composition exists. Otherwise it provides an approximate solution that maximizes the expected sum of values of user requests that can be serviced. The model studied although simple shades light on composition in stochastic settings and indeed we discuss several possible extensions

A coarse-grained Monte Carlo approach to diffusion processes in metallic nanoparticles

A kinetic Monte Carlo approach on a coarse-grained lattice is developed for the simulation of surface diffusion processes of Ni, Pd and Au structures with diameters in the range of a few nanometers. Intensity information obtained via standard two-dimensional transmission electron microscopy imaging techniques is used to create three-dimensional structure models as input for a cellular automaton. A series of update rules based on reaction kinetics is defined to allow for a stepwise evolution in time with the aim to simulate surface diffusion phenomena such as Rayleigh breakup and surface wetting. The material flow, in our case represented by the hopping of discrete portions of metal on a given grid, is driven by the attempt to minimize the surface energy, which can be achieved by maximizing the number of filled neighbor cells