Pushing and pulling electrons: the effect on the heat of formation of trifluoromethyl compounds

The effect on heats of formation, of conjoined or proximate functional groups which can interact via polar or resonance effects, is examined using the –CF₃ group as a standard. Two metrics are applied: the difference in heat of formation of G–CF₃ and G–CH₃, where –G is a wide range of functional groups, and also the deviation of the heat of formation of G–CF₃ from the average of the heats of formation of G–G and CF₃–CF₃. This latter metric reveals both stabilizing and destabilizing effects on the heat of formation, of up to 60 kcal/mol, depending on the polar and resonance nature of the –G structure. The possibility of using such metrics as a correction the group additivity values is examined.     

Development of a practical solid-phase synthesis approach to 1,3,5-triazepan-2,6-diones

1,3,5-Triazepan-2,6-diones are a class of conformationally restricted heterocycles derived from dipeptides. With the aim to develop a general and practical method useful for library production, three polymer-assisted syntheses, all based on a catch and release approach, have been evaluated and compared. The method involving a Hofmann rearrangement of N-Boc dipeptide carboxamides and subsequent trapping of the isocyanate on polymer-supported N-hydroxysuccinimide (PS-HOSu) was found to be the most reliable and versatile, allowing rapid access to the 1,3,5-triazepan-2,6-dione skeleton.     

On the relationship between fluctuating irreversible thermodynamics and “extended” irreversible thermodynamics

The relationship between fluctuating irreversible thermodynamics and theories of irreversible processes which include the thermodynamic fluxes as independent variables is explored. It is shown that the usual fluctuating linear theory of irreversible thermodynamics is a contraction of the extended theory. This contraction contains non-Markovian effects dependent upon the relaxation times associated with the thermodynamic fluxes. In the limit that these relaxation times are small, the extended theory is shown to be equivalent to the usual fluctuating thermodynamic theory. A critique of the extended theories is given from the point of view of the mechanistic statistical theory of irreversible processes.     

Geometry of equilibrium configurations in the Ising model

We derive microscopically precise identities for the geometry of small clusters in the equilibrium states of the two-dimensional Ising model with emphasis on near-critical phenomena.     

The 2880-Å emission spectrum of I2: Ion-pair states near 47 000 cm−1

An emission system of I₂ in Ar in the region 2830–2890 Å is examined under high resolution and found to display fine violet-degraded band structure. This system is interpreted as a charge-transfer transition originating from an ion-pair state near 47 000 cm^?1 and terminating on a weakly bound state which dissociates to two ground-state atoms. This interpretation is supported by spectral simulations employing a bound-free model. The transition is tentatively assigned as $\text{0}{}_{\mathrm{<mtext>g</mtext>}}{}^{\mathrm{?}}\text{→ 2431 0}{}_{\mathrm{<mtext>u</mtext>}}{}^{\mathrm{?}}\text{(}{}^3\text{Π}\text{)}$, according to which the excited state becomes the fourth ion-pair state near 47 000 cm^?1 to be experimentally characterized, and the lower state is the last component of the lowest ³Π state to be identified. The vibrational assignments include about 45 bands in ¹²⁷I₂ and ¹²⁹I₂, spanning v′ = 0–4 and v″ = 6–19, but with the numbering of the lower state remaining uncertain by several units. The main spectroscopic constants for the excited state are T_e = 47 070 cm^?1, ?_e = 105.7 cm^?1, ?_ex_e = 0.49 cm^?1. The spectral simulations place the lower state's potential curve 34 650 cm^?1 below the upper state at R = R′_e, with slope ?850 cm^?1/Å. For our “best” numbering of the lower state, ?_e = 20.5 cm^?1, ?_ex_e = 0.29 cm^?1, T_e = 12 190 cm^?1, and D_e = 360 cm^?1.     

Equilibrium statistics of a vortex filament with applications

The thermodynamic functions and scaling exponents (including the Kolmogorov and Flory exponents) of a vortex filament in thermal equilibrium are calculated, giving a quantitative content to earlier qualitative analyses. The numerical results uncover a percolation property of vortex filaments near the maximum entropy state. The implications of the results for the onset of turbulence, for the structure of its inertial range, and for superfluid vortices are discussed. In particular, it is shown that vortex stretching pushes a vortex system to a polymeric state and a Kolmogorov spectrum.This work was supported in part by the Applied Mathematical Sciences subprogram of the Office of Energy Research, U.S. Department of Energy, under contract DE-AC03-76SF-00098, and in part by the National Science Foundation under grant number DMS89-19074     

An Edge Server Placement Method Based on Reinforcement Learning

In mobile edge computing systems, the edge server placement problem is mainly tackled as a multi-objective optimization problem and solved with mixed integer programming, heuristic or meta-heuristic algorithms, etc. These methods, however, have profound defect implications such as poor scalability, local optimal solutions, and parameter tuning difficulties. To overcome these defects, we propose a novel edge server placement algorithm based on deep q-network and reinforcement learning, dubbed DQN-ESPA, which can achieve optimal placements without relying on previous placement experience. In DQN-ESPA, the edge server placement problem is modeled as a Markov decision process, which is formalized with the state space, action space and reward function, and it is subsequently solved using a reinforcement learning algorithm. Experimental results using real datasets from Shanghai Telecom show that DQN-ESPA outperforms state-of-the-art algorithms such as simulated annealing placement algorithm (SAPA), Top-K placement algorithm (TKPA), K-Means placement algorithm (KMPA), and random placement algorithm (RPA). In particular, with a comprehensive consideration of access delay and workload balance, DQN-ESPA achieves up to 13.40% and 15.54% better placement performance for 100 and 300 edge servers respectively.     

Science at the Hard X-ray Diffraction Limit (XDL2011), Part 1

There is growing excitement in the synchrotron materials science community about the potential of nearly diffraction-limited, high-repetition rate, hard X-ray sources, such as an Energy Recovery Linac (ERL) or an Ultimate Storage Ring (USR), and that these sources will pave the way to scientific insights and discoveries not possible with existing facilities. These future sources will deliver highly coherent, nearly diffraction-limited X-ray beams that will power ultra-intense, nanometer-scale X-ray probes and imaging capabilities approaching atomic resolution. They will produce X-ray pulses at MHz to GHz repetition rates and span pulse durations from below 50 femtoseconds to tens of picoseconds, enabling new classes of experiments in hard X-ray science.     

Lattice systems with a continuous symmetry

We consider perturbations of a massless Gaussian lattice field on ? ^d ,d≧3, which preserves the continuous symmetry of the Hamiltonian, e.g., $$ - H = \sum\limits_{< x,y > } {(\phi _x - \phi _y )^2 + T(\phi _x - \phi _y )^4 ,\phi _x \in \mathbb{R}.} $$ It is known that for allT>0 the correlation functions in this model do not decay exponentially. We derive a power law upper bound for all (truncated) correlation functions. Our method is based on a combination of the log concavity inequalities of Brascamp and Lieb, reflection positivity and the Fortuin, Kasteleyn and Ginibre (F.K.G.) inequalities.