Ab initio studies of the protonation of CO,N2 and NO+: Calculation of the minimum energy reaction paths

Ab initio molecular orbital calculations employing a 4-31G basis set have been used to study the minimum energy paths for the formation of HCO⁺, COH⁺, and HCOH²⁺ from CO by protonation. The protonation of N₂ to give NNH⁺ and HNNH²⁺ and of NO⁺ to form HNO²⁺ and NOH²⁺ have also been investigated. All species formed have linear equilibrium geometries and the minimum energy path for approach of the proton is along the line-of-centers of the heavy atoms. Energy barriers to the formation of the various species are given, where appropriate, and changes in geometry, ordering of molecular orbitals and orbital occupancy are discussed.     

4度循环图的不交路及k-宽直径

研究了4度循环图,构造出其任意两点之间的四条内部点不交路,并且给出其宽直径的一个较好的上界。     

Adaptive quality of service‐based routing approaches: development of neuro‐dynamic state‐dependent reinforcement learning algorithms

In this paper, we propose two adaptive routing algorithms based on reinforcement learning. In the first algorithm, we have used a neural network to approximate the reinforcement signal, allowing the learner to take into account various parameters such as local queue size, for distance estimation. Moreover, each router uses an online learning module to optimize the path in terms of average packet delivery time, by taking into account the waiting queue states of neighbouring routers. In the second algorithm, the exploration of paths is limited to N‐best non‐loop paths in terms of hops number (number of routers in a path), leading to a substantial reduction of convergence time. The performances of the proposed algorithms are evaluated experimentally with OPNET simulator for different levels of traffic's load and compared with standard shortest‐path and Q‐routing algorithms. Our approach proves superior to classical algorithms and is able to route efficiently even when the network load varies in an irregular manner. We also tested our approach on a large network topology to proof its scalability and adaptability. Copyright © 2006 John Wiley & Sons, Ltd.     

A hierarchical Path Computation Element (PCE)-based k-random-paths routing algorithm in multi-domain WDM networks

We propose an inter-domain routing algorithm for multi-domain wavelength-division multiplexing (WDM) mesh networks. On the basis of the hierarchical Path Computation Element (PCE) architecture, the proposed algorithm introduces a k random path strategy in the parent PCE to adjust the algorithm optimization level. Simulation results indicate that the proposed algorithm outperforms previous schemes in terms of blocking probability and resource utilization, while preventing the increase in PCEP signaling overhead.     

TOPOLOGICAL CONDITIONS FOR SOLVA ILITY OF PSEUDO-TEARING SUBNETWORK

The problem for the solvability of pseudo-tearing subnetwork is one of the essentialinvestigations of network theory.The results presented would be not only mathematical conditionsbut also topological conditions for subnetwork solvability.These conditions are necessary andalmost sufficient.It should guide one intuitively to the design of accessible nodes.     

Reaction paths of some open-shell reactive intermediates

The intermolecular interaction energy for reacting systems in singlet, triplet and doublet states was partitioned by the perturbation expansion method into the chemically meaningful five interaction terms: the Coulomb, exchange-repulsion, induction, dispersion, and charge-transfer energies. In the local ZDO approximation, these energy terms were evaluated for the dimerization of methylenes (^1,3CH₂), the additions of carbenes (^1,3CH₂ and^1,3CF₂) as well as amino radicals (²NH₂ and²NF₂) toward ethylene, and the hydrogen abstractions by methylenes (^1,3CH₂), nitrene (³NH), and hydroxyl radical (²OH) from methane. It has been found that the reaction path is much influenced by the spinmultiplicity, and that the charge-transfer and exchange-repulsion terms play a dominant role in determining the course of reactions.     

Bifurcations and transition states

Bifurcations of reaction channels are related to valley-ridge inflection points and it is examined what happens when these do not coincide with transition states. Under such conditions there result bifurcating regions. There exist a number of different prototypes for such regions which are discussed explicitly on the basis of the pertinent Taylor expansions. When bifurcations occur close enough to transition states then there result bifurcating transition regions. An example for a bifurcating transition region is exhibited which is obtained from a quantum mechanical ab initio calculation for the ring opening of cyclopropylidene to aliene. In general there exist no orthogonal trajectory patterns which could serve as simplified models for channel bifurcations.Operated for the U.S. Department of Energy by Iowa State University under Contract No. W-7405-ENG-82. This work was supported by the Office of Basic Energy Sciences     

Location of saddle points and minimum energy paths by a constrained simplex optimization procedure

Two methods are proposed, one for the location of saddle points and one for the calculation of steepest-descent paths on multidimensional surfaces. Both methods are based on a constrained simplex optimization technique that avoids the evaluation of gradients or second derivative matrices. Three chemical reactions of increasing structural complexity are studied within the PRDDO SCF approximation. Predicted properties of reaction hypersurfaces are in good overall agreement with those determined by gradient minimization and gradient following algorithms in connection with various ab initio SCF methods. Computational efforts required by the new procedures are discussed.     

Gradient extremals and valley floor bifurcations on potential energy surfaces

Gradient extremals are curves in configuration space denned by the condition that the gradient of the potential energy is an eigenvector of the Hessian matrix. Solutions of a corresponding equation go along a valley floor or along a crest of a ridge, if the norm of the gradient is a minimum, and along a cirque or a cliff or a flank of one of the two if the gradient norm is a maximum. Properties of gradient extremals are discussed for simple 2D model surfaces including the problem of valley bifurcations.     

Metric and ultrametric spaces of resistances

Consider an electrical circuit, each edge e of which is an isotropic conductor with a monomial conductivity function . In this formula, y_e is the potential difference and current in e, while μ_e is the resistance of e; furthermore, r and s are two strictly positive real parameters common for all edges. In particular, the case r=s=1 corresponds to the standard Ohm’s law.In 1987, Gvishiani and Gurvich [A.D. Gvishiani, V.A. Gurvich, Metric and ultrametric spaces of resistances, in: Communications of the Moscow Mathematical Society, Russian Math. Surveys 42 (6 (258)) (1987) 235-236] proved that, for every two nodes a,b of the circuit, the effective resistance μ_a,b is well-defined and for every three nodes a,b,c the inequality holds. It obviously implies the standard triangle inequality μ_a,b≤μ_a,c+μ_c,b whenever s≥r. For the case s=r=1, these results were rediscovered in the 1990s. Now, after 23 years, I venture to reproduce the proof of the original result for the following reasons:

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It is more general than just the case r=s=1 and one can get several interesting metric and ultrametric spaces playing with parameters r and s. In particular, (i) the effective Ohm resistance, (ii) the length of a shortest path, (iii) the inverse width of a bottleneck path, and (iv) the inverse capacity (maximum flow per unit time) between any pair of terminals a and b provide four examples of the resistance distances μ_a,b that can be obtained from the above model by the following limit transitions: (i) r(t)=s(t)≡1, (ii) r(t)=s(t)→∞, (iii) r(t)≡1,s(t)→∞, and (iv) r(t)→0,s(t)≡1, as t→∞. In all four cases the limits μ_a,b=lim_t→∞μ_a,b(t) exist for all pairs a,b and the metric inequality μ_a,b≤μ_a,c+μ_c,b holds for all triplets a,b,c, since s(t)≥r(t) for any sufficiently large t. Moreover, the stronger ultrametric inequality μ_a,b≤max(μ_a,c,μ_c,b) holds for all triplets a,b,c in examples (iii) and (iv), since in these two cases s(t)/r(t)→∞, as t→∞.

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Communications of the Moscow Math. Soc. in Russ. Math. Surveys were (and still are) strictly limited to two pages; the present paper is much more detailed.Although a translation in English of the Russ. Math. Surveys is available, it is not free in the web and not that easy to find.

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The last but not least: priority.